Determination of Migration Rates For Certain Phthalates: Survey of Chemical Substances in Consumer Products No. 149, 2016

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Determination of

Migration Rates for


Certain Phthalates
Survey of chemical substances in consumer
products No. 149, 2016
Title: Authors:

Determination of Migration Rates for Certain Nils H. Nilsson


Phthalates Jeanette Schjøth-Eskesen
Bjørn Malmgren-Hansen
Eva Jacobsen

Published by:

The Danish Environmental Protection Agency


Strandgade 29
DK-1401 Copenhagen K
www.mst.dk

Year: ISBN no.

2016 978-87-93529-01-4

Disclaimer:

The Danish Environmental Protection Agency publishes reports and papers about research and development projects
within the environmental sector, financed by the Agency. The content of this publication do not necessarily represent the
official views of the Danish Environmental Protection Agency. By publishing this report, the Danish Environmental
Protection Agency expresses that the content represents an important contribution to the related discourse on Danish
environmental policy.
Sources must be acknowledged.

2 Determination of Migration Rates for Certain Phthalates


Contents

Contents .................................................................................................................... 3

Preface ...................................................................................................................... 5

Summary and conclusion .......................................................................................... 6

Abbreviations and acronyms ................................................................................... 12

1. Introduction ..................................................................................................... 13
1.1 Background ........................................................................................................................13

1.2 Soft PVC..............................................................................................................................13

1.2.1 Properties of PVC raw material .........................................................................................13

1.2.2 Plastification of PVC ..........................................................................................................14

1.2.3 Comparison of soft PVC and rubber/TPE .........................................................................14

1.2.4 Other additives in soft PVC ............................................................................................... 15

1.2.5 Processing of soft PVC and formularies ............................................................................ 15

1.3 Rules for migration ............................................................................................................ 15

2. Factors affecting migration rates ...................................................................... 18


2.1 Physical and chemical properties of the five phthalates ................................................. 18

2.2 Knowledge on formulary ...................................................................................................21

2.3 History of samples .............................................................................................................21

2.4 Sample preparation ...........................................................................................................21

2.5 Methods for migration analysis .........................................................................................21

2.5.1 Formulary, history and homogeneity of the article ......................................................... 22

2.5.2 Surface/volume/density of the article ............................................................................. 22

2.5.3 Contamination of reagents, solvents, utensils, glassware etc. ........................................ 22

2.5.4 Static and dynamic tests ................................................................................................... 22


2.5.5 Artificial saliva and sweat ................................................................................................. 23

2.5.6 Extraction method and yield ............................................................................................ 24

2.5.7 Chromatographic analysis of contact simulant extracts ................................................. 25

3. Results of the literature search ........................................................................ 26


3.1 Method used for the literature search .............................................................................. 26

3.2 Migration rates of the five phthalates .............................................................................. 26

3.3 The analysis methods from the literature survey ............................................................ 30

3.3.1 Temperature and migration time ..................................................................................... 30

3.3.2 The static and dynamic tests used in the analysis methods ............................................ 30
3.3.3 Artificial saliva and sweat used in the literature ............................................................. 32

Determination of Migration Rates for Certain Phthalates 3


3.4 ECHA´s opinion and conclusions based on available literature regarding DINP
migration rates to artificial saliva ..................................................................................................... 33

3.5 Methodology for proposal of migration rates .................................................................. 35

3.5.1 Dynamic force ................................................................................................................... 36

3.5.2 Physical and chemical parameters ................................................................................... 37

3.5.3 Temperature and simulants ............................................................................................. 37

3.6 Migration rates proposed ................................................................................................. 38

4. References ....................................................................................................... 41

5. Appendix .......................................................................................................... 45
5.1 DEHP ................................................................................................................................. 45

5.1.1 Migration to artificial sweat ............................................................................................. 45

5.1.2 Migration to artificial saliva ............................................................................................. 49

5.2 DINP .................................................................................................................................. 52

5.2.1 Migration to artificial sweat ............................................................................................. 52

5.2.2 Migration to artificial saliva ............................................................................................. 52

5.3 DBP .....................................................................................................................................61

5.3.1 Migration to artificial sweat ..............................................................................................61

5.3.2 Migration to artificial saliva ............................................................................................. 63

5.4 DIBP .................................................................................................................................. 64

5.4.1 Migration to artificial sweat ............................................................................................. 64

5.4.2 Migration to artificial saliva ............................................................................................. 66

4 Determination of Migration Rates for Certain Phthalates


Preface

This report discusses the migration rates of the following five phthalates:

 Di(2-ethylhexyl) phthalate (DEHP)


 Diisononyl phthalate (DINP)
 Butyl benzyl phthalate (BBP)
 Di-n-butyl phthalate (DBP)
 Diisobutyl phthalate (DIBP)

The objective of this report is to identify and discuss the factors, which contribute to the
uncertainties of migration rates published in the available literature, and to discuss why there
seems to be no correlation between the migration rates and the concentration of phthalates in soft
PVC articles, as would be predicted by Fick´s law for diffusion.

The project was carried out by Danish Technological Institute (DTI).

The following employees have contributed to the project:

Nils H. Nilsson (project leader), DTI


Jeanette Schjøth-Eskesen, DTI
Bjørn Malmgren-Hansen, DTI
Eva Jacobsen, DTI

This project was financed by the Danish Environmental Protection Agency (EPA), and the contact
persons at Danish EPA were Shima Dobel and Toke Winther.

Determination of Migration Rates for Certain Phthalates 5


Summary and conclusion

The literature search covered essential literature from 1998 to 2015, with focus on literature from
Denmark. In addition to studies from Denmark, a few other studies from the Netherlands, Austria,
Sweden, Germany, Great Britain, Turkey, Canada, Japan and the United States were included.
Besides the studies on migration rates, a search was also carried out on literature that discusses the
results of the different migration studies.

It can be assumed that DEHP will have migration rates that are rather close to DINP because their
molecular weights and physical/chemical properties are close to each other and the water solubility
of both are extremely low (DINP < 1 µg/l and DEHP 3µg/l).

For DBP and DIBP, migration rates are expected to be much higher than for DEHP and DINP at the
same concentration level due to their lower molecular weight and higher solubility in aqueous
media (water, artificial sweat and saliva). However, in most cases the amount of these two
phthalates will be rather low (a few percent and probably less than 10 % w/w) as they according to
literature (Wilson, 1995) only are used as speciality plasticisers for facilitating the dispersion of the
main primary plasticisers such as DEHP and DINP. A rather high content has been found in some
consumer products (e.g. plastic sandals with 21.2 %w/w DIBP in Danish EPA no. 107 and training
ball with 35.4 %w/w DIBP in Danish EPA no. 109). In these cases, DBP and DIBP are cheap
primary plasticisers and the manufacturers have not tried to reduce the migration of phthalates.

BBP is mainly used for flooring and wallpaper and no migration rates have been found in the
literature search. BBP probably has migration rates in between DINP/DEHP and DBP/DIBP at the
same concentration level based on the solubility parameter, chemical structure and water solubility.
It should be remembered that wear and tear is an important parameter for flooring and exposure
from BBP can take place by dust generated in daily use.

It is not possible to determine one realistic migration rate for each of the five phthalates which will
always be valid, since the migration rate of phthalates in soft PVC seems to be depending on many
different factors such as the solubility of the given phthalate, the phthalate content in the specific
product and other chemical and physical parameters.

The purpose of this report is to suggest migration rates for each of the five selected phthalates in
soft PVC, which can be used for risk assessment purpose, in cases where the specific migration rate
has not been measured. The suggested migration rates are based on numerous migration studies
from the accessible literature.

One of the major factors on the migration rate is the way the migration analysis is carried out.
Therefore, very different results were obtained depending on how vigorous the applied dynamic
forces were. Due to that major factor, it has been necessary to divide the proposed migration rates
according to the experimental set-up used.

Denmark, Austria and the United States use mild static or dynamic methods. The Netherlands have
another dynamic method compared to Denmark, Austria and the United States that give higher
migration rates but the migration rates are still below in vivo tests in adults. In contrast, Japan use
very harsh dynamic tests in an attempt to obtain results in line with the in vivo test results obtained

6 Determination of Migration Rates for Certain Phthalates


in voluntary adults to simulate children’s mouthing and chewing on soft PVC products. This
approach can be questioned, as it is not obvious that the adult in vivo measurements are the
realistic values for migration for simulating children’s exposure by sucking and chewing.

To our knowledge it is on a scientific base not possible to compare the conditions (chewing) of
adults with the chewing/mouthing of children, as the oral cavity (e.g. musculature) of a child’s
mouth is not fully developed. Therefore, the chewing force of children is expected to be weaker than
for adults. In addition, the stimulation of the saliva production by chewing might be different for
children compared with adults. It can be questioned if the results from the in vivo adult studies are
the true value for phthalate migration rates1.

The analytical methods to determine the migration of phthalates are therefore divided into three
categories: mild, medium and harsh conditions as seen in table 1. The mild conditions result
generally in lower migration rates compared with the in vivo adult migration rates for the
simulation of children’s sucking and chewing on soft PVC products. The head over heels method
(HOH) is judged as the most documented method of all, mostly for the migration rates for DINP to
artificial saliva, but also a few for DEHP. The HOH method seems to be the most realistic method,
since the given product is rotated once per second, which resembles how a child will chew on a toy.
In addition, the test conditions such as temperature resemble the human body temperature at 37°C.
For this reason and because the other methods are very different in their approach, the HOH
method is recommended as the reference method for the determination of migration rates for
phthalates well knowing that realistic migration rates are difficult to determine in in vitro or adult
in vivo studies.

Compared with the mild methods based on static tests or dynamic tests using mild shaking or
magnetic stirring the migration rates for the HOH method will be higher. Static tests will most
likely give too low results, since products e.g. sandals and pacifiers will be in movement while being
used.

When the migration rates are used for risk assessment purposes, a high migration rate will result in
a more conservative risk assessment. The harsh method used by the Japanese studies seem far
from reality by using dynamic test at 300 rpm and is judged to give too high migration rates.

As the HOH method first of all has been most documented for DINP the migration rates for the
other phthalates have been determined by using a correction factor based on the mild migration
studies or/and taking the chemical/physical properties of the phthalates in consideration
(molecular weight, solubility in water, log Kow, vapour pressure and δD (solubility parameter)).

TABLE 1
ANALYSIS METHODS DIVIDED INTO DIFFERENT CONDITIONS

Analysis method

Mild Static or dynamic conditions at 37±3°C (DK, A, TR, U.S.A.)

Medium Head over heels method (NL) at 60 rpm

Harsh Horizontal shaking at 300 rpm (J)

No migrations rates were found for BBP in the reviewed migration studies from the literature
search. BBP was analysed for and detected in some products (e.g., sandals in the Danish EPA report
no. 107, 2010 - Phthalates in plastic sandals), but the content of BBP was below the detection limit
in most quantitative characterisations and in all the migration studies. This is as expected, as the

1 Conferred with Professor Dorte Haubek, Aarhus School of Dentistry, Aarhus the 7th December 2015.

Determination of Migration Rates for Certain Phthalates 7


most common use is for flooring and wallpaper. It is expected that the migration rate of BBP would
be similar or a little lower than DBP and DIBP due to the similar solubility parameter (δD) and
partition coefficient (Kow). Wormuth et al. 2006 and Wormuth 2006b listed migration rates for BBP
(average migration rate was 0.002 µg/cm2/min and 0.02 µg/cm2/min respectively), but it was not
possible to find the original reference with product information and analysis method.

Figure 1-4 give an overview of the results from the literature survey with the migration rates of the
other four phthalates as a function of phthalate content.

FIGURE 1
MIGRATION RATE AS A FUNCTION OF DEHP CONTENT (%W/W) FOR THE MILD CONDITIONS (LEFT GRAPH) AND
MEDIUM AND HARSH CONDITIONS (RIGHT GRAPH)

Medium
DEHP Mild DEHP
Harsh
4
Migrationrate [µg/cm2/h

Migration rate [µg/cm2/h]


120

3 100
80
2 60
40
1
20

0 0
0 20 40 60 0 20 40 60

Content [w/w%] Content [% w/w]

FIGURE 2
MIGRATION RATE AS A FUNCTION OF DINP CONTENT (%W/W) WITH MILD CONDITIONS (LEFT GRAPH) AND
MEDIUM AND HARSH CONDITIONS (RIGHT GRAPH)
Medium
DINP Mild DINP
Harsh
14 140
Migration rate [µg/cm2/h]
Migration rate [µg/cm2/h]

12 120
10 100
8 80
6 60
4 40
2 20
0 0
0 10 20 30 40 0 20 40 60
Content [% w/w] Content [% w/w]

FIGURE 3

8 Determination of Migration Rates for Certain Phthalates


MIGRATION RATE AS A FUNCTION OF DBP CONTENT (%W/W) WITH MILD CONTIDIONS (LEFT GRAPH) AND HARSH
CONDITIONS (RIGHT GRAPH)

DBP Mild DBP Harsh

0,7 160
Migrtionrate [µg/cm2/h]

Migrtionrate [µg/cm2/h]
0,6 140

0,5 120
100
0,4
80
0,3
60
0,2 40
0,1 20
0 0
0 10 20 30 40 0 5 10
Content [% w/w] Content [% w/w]

FIGURE 4
MIGRATION RATE AS A FUNCTION OF DIBP CONTENT (%W/W) FOR MILD CONDITIONS

DIBP
7
Migrationrate [µg/cm2/h]

6
5
4
3
Mild
2
1
0
0 10 20 30 40
Content [% w/w]

The migration rates illustrated in the figures above have no clear correlations to the content of
phthalates. The average migration rates are divided into the mild, medium and harsh analytical
method conditions. The results have then been subdivided in minimum, mean and maximum
values similar to Wormuth et al., 2006. The mean is obtained by taking all the mean values from the
studies in the three conditions. The results are in the unit µg/cm2/h.

TABLE 2
MIGRATION RATES FOR THE MILD ANALYTICAL METHOD CONDITIONS

Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 0.002 0.27±0.62 3.31

DINP 0.09 1.61±2.80 13.3

DBP 0.001 0.17±0.24 0.66

DIBP 0.04 0.77±1.39 5.80

Determination of Migration Rates for Certain Phthalates 9


TABLE 3
MIGRATION RATES FOR THE MEDIUM ANALYTICAL METHOD CONDITIONS

Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 0.04 10.7±7.99 31.3

DINP 1.5 13.3±6.44 29.1

DBP - - -

DIBP - - -

TABLE 4
MIGRATION RATES FOR THE HARSH ANALYTICAL METHOD CONDITIONS

Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 4.4 54.6±41.0 118

DINP 7.8 44.8±33.4 124.8

DBP 1.17 48.5±46.9 144.8

DIBP - - -

Calculations have been made in order to estimate migration rates for the five phthalates. The basis
is the HOH method, since this method seems to give the most realistic migration rates, as the
product is rotated once per second, resembling the use of a product. The HOH method is also the
most documented for DINP to artificial saliva and the other methods make use of very diverse
experimental conditions which make comparison difficult. The migration rates for the remaining
four phthalates are based on the results from the mild migration studies by using a correction factor
and/or taking the chemical-physical properties of the individual phthalates in consideration
(molecular weight, solubility in water, log Kow, vapour pressure and δD (solubility parameter)). For
statistical reasons the HOH results were only based on DINP, since migration rates for DEHP were
only measured a few times by HOH and migration rates for the three other phthalates were not
measured by HOH.

At present as far as the many studies for migration of phthalates have been carried out in very
different ways it shall be recommended to use the following migration rates for calculation of risk of
exposure to the phthalates until further evidence is available:

TABLE 5
ESTIMATED MIGRATION RATES FOR THE FIVE PHTALATES

DEHP DINP DIBP DBP BBP

Migration rate (µg/cm2/h) 10 13 13 13 12

The estimated migration rates are quite close to each other. The migration rates for DIBP and DBP
should in theory be higher than the migration rates for DINP and DEHP if the content of the
phthalates in the products are similar. The reason for the similar migration rates estimated is that

10 Determination of Migration Rates for Certain Phthalates


the concentrations of DIBP and DBP in most cases are lower than the concentration of DEHP and
DINP in the products. Even though results indicate that there is no correlation between the content
and migration, very low contents of phthalates are expected to give relatively lower migration rates.
This could also explain why the results are not compatible with Wormuth et al., 2006, because there
are low concentrations of the phthalates in the products and these are most likely added as a
processing aid before adding DEHP or DINP, but still have a softening effect. In Wormuth et al.,
2006 it is also stated that only samples with low DIBP content are considered. According to Fick’s
law the migration rate will depend on the concentration level, therefore without knowing the
phthalate content, it is difficult to compare the listed migration rates in table 5 with the results
found from Wormuth et al., 2006.

A more in-depth discussion in ECHA, 2013 of the data for migration rates of DINP to artificial
saliva has led to the conclusion that the migration rate from mouthing of toys will be an in vitro
migration rate of 45 µg/cm2/h, measured for a plate with a content of 40.7% w/w DINP and a
typical in vivo estimate will be 14 µg/cm2/h. The latter value of the migration rate is based on taking
the mean of all the means from the in vivo studies. It is not evident why the in vivo results are lower
than the in vitro result, but it is very interesting that our proposal for in vitro migration rates are
comparable with the in vivo results from ECHA, 2013.

The above calculated migration rates do not consider the possible of using cosmetic products such
as sun oil and other skin care products or fatty emulsions from e.g. milk and vegetable fat present in
when making risk assessments. This would increase the migration rates as seen in the Danish EPA
no. 107, 2010.

The method described in DS/EN 71-10 by using pure water as the simulant for both sweat and saliva
should be considered to use in a standardized migration method. Carrying out the migration step at
20 °C for 1 hour is recommended for practical reasons in the standard instead of 37° C, as this does
not seem to have a significant effect on the migration rate compared to other alterations, but still
having in mind that migration rates will increase with temperature.

The correlation between in vivo and in vitro migration rates is not obvious. In one study the
migration rate for DINP to artificial saliva was much higher in vitro than in vivo (Niino, 2003), but
in another study the in vivo migration rate was a factor (in mean) 39.5 higher than the in vitro
migration rate (Babich, 1998). In both studies, many factors influencing the migration rates have
been discussed and it can be questioned as discussed above how valid “real” migration rates
(determined in vivo) are to the true migration rate for children who chew and suck on soft PVC
toys. It has to be mentioned that saliva might contain fatty emulsions from ingestion of food, e.g.,
milk and vegetable fat, and from contact with suntan lotion and fat/oil-containing cosmetics and
the migration can increase several orders from 5 – 1000 times.

Determination of Migration Rates for Certain Phthalates 11


Abbreviations and acronyms

A Austria
ACN Acetonitrile
BBP Butyl Benzyl Phthalate
BfR Bundesinstitut für Risikobewertung
BnBzO Benzoic acid Benzyl ester
Bs British Standard
CSTEE Scientific Committee on Toxicity, Ecotoxicity and the Environment
DBP Dibutyl phthalate
DCM Dichloro Methane
DEHP Di(2-ethylhexyl) Phthalate
DINP Diisononyl Phthalate
DK Denmark
DOP Di(2-ethylhexyl) Phthalate
DS Danish Standard Organization
ECHA The European Chemicals Agency
EN European Norm
EPA Environmental Protection Agency
GC/MS Gas Chromatography with Mass Spectroscopy detection
HOH Head Over Heels
HPLC High Pressure Liquid Chromatography
HPTLC High Performance Thin Layer Chromatography
ISO International Standardization Organisation
J Japan
JRC Joint Research Centre
Log Pow The logarithm to the partition coefficient between octanol and water. Also known
as Log Kow.
LOUS Danish List of Undesirable Substances
NL Netherland
PVC Polyvinyl Chloride
SOP Standard Operating Procedure
tg Glass Transition Temperature
THF Tetrahydrofuran
TPE Thermo Plastic Elastomer
TR Turkey
U.S.A. United States of America
δD Solubility Parameter
% w/w Weight Percentage

12 Determination of Migration Rates for Certain Phthalates


1. Introduction

1.1 Background
Over the years, the Danish Environmental Protection Agency (EPA) has completed a number of
projects involving studies on the migration rate of phthalates, in many cases from “worst-case”
scenarios. The “worst-case” scenarios are set up based on the use of the products and the direct
contact with the products either via skin contact or mouthing. These studies have involved a
number of different consumer products with these five phthalates in focus, where the content in the
products and the migration have been quantified. Surprisingly there does not seem to be a readily
correlation between the concentration of phthalates in the products and the migration rates of the
phthalates.

For international studies, the situation is the same. It is not possible to make a correlation between
the content of phthalates and the migration rates.

The purpose of this report is to suggest migration rates for specific phthalates in soft PVC. The
suggested migration rates will be based on numerous migration studies from the accessible
literature. The background to the varying migration rates will be investigated, discussed and
evaluated. Based on the evaluation suggested migration rates will be established without having to
conduct actual migration analyses.

The focus in this report will only be on the migration of the following phthalates: di(2-ethylhexyl)
phthalate (DEHP), diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), di-n-butyl phthalate
(DBP) and diisobutyl phthalate (DIBP) from soft PVC that are in contact with artificial sweat or
saliva simulants. Comparison with in vivo studies will be included when they exist.

These five phthalates are studied, because DEHP, BBP, DBP and DIBP are part of ECHA’s
authorisation scheme and that DINP is one of the most used phthalates in soft PVC.

This report will highlight the factors and parameters that will influence the analytical determination
of the migration rates for the five phthalates to artificial saliva and artificial sweat and the
uncertainties they may contribute with in the calculations of the migration rates.

1.2 Soft PVC

1.2.1 Properties of PVC raw material


Soft polyvinyl chloride (PVC – Illustrated in Figure 1) - also called plasticised or flexible PVC -
covers a very broad and manifold variety of formularies (recipes) that have different physical and
mechanical properties. Soft PVC can be processed by nearly all methods used for thermoplastics.

FIGURE 5
ILLUSTRATION OF THE REPEATING UNIT OF PVC

Determination of Migration Rates for Certain Phthalates 13


The raw material of PVC is rigid and brittle with a glass transition temperature tg = 80 °C to 107 °C
(Wypych, 2015). Below tg, the amorphous regions of a polymer are in the glassy state and the
polymeric PVC molecules are nearly motionless which means that the polymer below tg generally is
hard, brittle and rigid. It is produced by chlorination of ethylene and the raw material is most
commonly sold as a powder. The PVC raw polymer has a weight average molecular weight of
between 70,000 and 500,000+ g/mol. The low molecular weight PVC resins aid the melting process
and they can be used for high filler compositions, e.g., calcium carbonate.

In literature, PVC is described as an amorphous plastic material, but in fact there are small regions
in well-arranged order within the polymeric structure, and the “crystallinity” of PVC is in the range
of 0.5% to 10% and has a melting point of 285 °C (Wypych, 2015).

1.2.2 Plastification of PVC


The raw material of PVC becomes soft by adding plasticisers to the PVC in amounts of up to 50%
w/w or even more. The typical range for soft PVC is 30 – 50% w/w (Baur et al., 2007). The most
common plasticisers are phthalates of orthophthalic acid with linear or branched alcohols on the
carbon chain (often on the seventh carbon (C7) to the thirteenth carbon (C13)). For many years,
DEHP has been the most used plasticiser for PVC accounting for 65 – 70% of the world market
(Baur et al., 2007). After the classification of DEHP as toxic for reproduction, DEHP was
substituted for many uses and the use of DINP raise. DEHP, DBP and BBP have been restricted in
toys and childcare articles in EU since 2007 and DINP has been restricted in toys and childcare
articles that can be put in the mouth since 2007 (REACH Annex XVII, Entry 51 and 52). In
addition, DIBP is restricted in toys (Toy Safety Directive 2009/48/EC) in concentrations above the
classification limit.

The tg of soft PVC depends on the amount of plasticiser. The higher the amount of plasticiser, the
lower the tg. For example, PVC with a content of 30%w/w DEHP has a tg = 0 °C depending on the
additives used in the PVC (Wypych, 2015). The hardness of soft PVC, measured as Shore A, is often
used to characterize the soft PVC with regard to brittleness. In the range 60 – 70 Shore A, which
also is typical for rubber, the soft PVC becomes brittle in the temperature interval -30°C to -50 °C
(Baur et al., 2007)

The amorphous part of PVC accepts the plasticisers, while the ordered structure (“crystallites”)
preserves the structure. In order to fuse the main plasticiser (e.g., DEHP and DINP with rigid PVC)
it is common practice to add phthalates like DBP and DIBP in the mixing process. DBP and DIBP
will make the PVC swell as they have a solubility parameter closer to PVC than the main plasticisers
do. This will lower the viscosity and make processing faster. It has not been possible to find
information on how much DBP and DIBP is added to the formularies for soft PVC, but it is
estimated to be low due to the higher tendency to migrate compared to DEHP and DINP because
the molecules are smaller (around 5 – 15 % w/w). To maintain the physical properties of PVC it is
important that the plasticisers do not destroy the crystalline part of the PVC, but solely enter the
amorphous phase (Wilkes et al., 2005). However the literature studies surprisingly reveal that in
some consumer products rather high amounts (10 – 35 % w/w) of DBP and DIBP is used e.g.
sandals and balls.

1.2.3 Comparison of soft PVC and rubber/TPE


In many ways, soft PVC behaves like rubber. A comparison to TPEs (thermoplastic elastomers) is
fair, as TPEs also behave like rubber due to the crystalline regions in the polymer molecular
structure that imitates the chemical crosslinks in rubber. Soft PVC and TPEs can be melted again at
temperatures above the melting point of the crystallites. That is not possible with rubber, due to the
chemical bonds between the rubber polymer chains.

14 Determination of Migration Rates for Certain Phthalates


1.2.4 Other additives in soft PVC
Besides the plasticisers, the soft PVC formularies can contain a number of other additives such as
stabilisers, lubricants, fillers, colorants, blowing agents and viscosity regulators, but in smaller
amounts than the plasticisers. The filler content often ranges from 30 – 40% w/w in soft PVC.

Thermal stabilisers are the most important additives used in soft PVC besides the plasticisers and
the fillers and are always part of the formularies. They are typically added in concentrations from
0.05 – 5% w/w. The thermal stabilisers are a group of different chemical substances. Important
types are barium/calcium/zinc carboxylates, butyltin-based substances, epoxidised soybean oil and
different organic phosphites. Synergy exists between these different substances and their function is
to protect the PVC during processing by preventing oxidation and liberation of hydrogen chloride.

1.2.5 Processing of soft PVC and formularies


Soft PVC can be processed either through a melting process or as plastisols. The former most
common melting processes are extrusion, calendaring and injection moulding. The latter are
dispersions of the solid particulate components (mainly PVC emulsion resins) of a formulation in
the mixed liquid component (mainly plasticisers). The main application of melted PVC is for
construction, rigid pipes and wire and cable insulation. The main large-scale applications of
plastisols comprise wallpaper, cushion vinyl flooring, upholstery, carpet backing and unsupported
PVC for car interior trims. The plastisols are stable until 35 °C, but when heated to 150 – 220 °C
they obtain the typical properties of soft PVC (Baur et al., 2007).

Table 6 shows an example of a formulary for toys from 1997, where DEHP was not yet banned for
use in toys. Today non-orthophthalate ester plastisicers are often used instead, for example di(2-
ethylhexyl) adipate and acetyl tributyl citrate (Report to the U.S. Consumer Product Safety
Commission, 2014).

TABLE 6
EXAMPLE OF A FORMULARY FOR TOYS FROM 1997 (WYPYCH, G. 2015)

Raw material Concentration, parts

PVC dispersion resin 50

PVC blending resin 50

DEHP 81

2,2,4-Trimethyl-1,3-pentanediol diisobutyrat 9

Epoxidised soybean oil 5

Stabiliser 3

In the PVC formulary (Wypych, 2015), around 600 formularies for soft PVC for different
applications are recorded. However, it is estimated that several thousand formularies exist and they
are most frequently used for technical articles and not for toys.

1.3 Rules for migration


The migration rate depends on a number of parameters such as size, molecular weight, chemical
bonds, solubility and initial concentration in the plastic polymer. It can be complicated to
determine the migration rate of phthalates from soft PVC, since they are not covalently bonded to
the polymer chain. Therefore, the migration rate depends both on the properties of the plastic as
well as on the properties of the specific phthalate.

Determination of Migration Rates for Certain Phthalates 15


The migration rate of organic chemical substances depends to a large degree on the size. The boiling
points for a phthalate increase as the number of carbons increase in the ester groups. Small
molecules, typically monomers and residual solvents, will migrate fast as they often have a low
boiling point and a small molecular size, which makes it easier to travel through the amorphous
phase of the plastic polymer because they need less space to find pathways in the polymeric plastic
structure. For the five phthalates studied, the higher molecular weight chemical substances are
bigger molecules. This means that they demand more space in the amorphous plastic structure
since the molecule is larger. For this reason, the migration rate will slow down for chemical
substances with similar chemical structures.

The molecular weight of substances used as additives in plastic are estimated to be in the range of
200 – 2000 g/mol. The five phthalates in this study have a molecular weight in the range of 278 to
404 g/mol and will migrate faster than high molecular weight components.

Another requirement for the additives is that the solubility of the additive in the plastic should be
high, but low in a liquid in contact with the plastic. That can be judged by log Pow (log K ow) or the
solubility data (solubility parameters δ). As originally defined, δ is directly related to the cohesive
energy density, and different materials are mutually compatible when they have similar values of δ.
The solubility of the five phthalates in water especially for DEHP and DINP are very low, and
therefore the tendency to migrate to a water based simulant like artificial saliva or sweat will be low.
This means that the migration rates for the discussed phthalates will be low or even undetectable in
static in vitro experiments if the migration alone is based on the water solubility of the phthalates.
However, migration is not only governed by the water solubility but also by the volatility depending
on their chemical structure and boiling point.

The initial concentration of the chemical substance in the plastic, the thickness of the plastic item,
the crystallinity of the plastic and the surface structure of the plastic item will influence the
migration rate in a rather complex way, but the main route to migration is via the amorphous
regions in the plastics. PVC is considered amorphous, but as mentioned earlier it has regions of
some ordered structure (crystallites), which plays a major role for the properties of soft PVC.

The flux J of substances (additives) from plastics (in this case migration of plasticisers from soft
PVC) obeys Fick’s law:

𝑑𝐶
𝐽 = −𝐷 ∙
𝑑𝑥

where D is the diffusion coefficient of the substance, J is the flux (mole of substance per time unit)
and dC/dx is the concentration difference of the substance over the diffusion distance.

The flux J will decrease over time when the concentration in the product decreases and the
diffusion coefficient D will depend on the temperature according to an Arrhenius relation

𝐸
𝐷 = 𝐾 ∙ 𝑒 −𝑅𝑇

The flux can be integrated over time to a total migration M.

For a given time and temperature the total migration can be modelled according to:

𝐸
𝑀 = 𝐶0 ∙ 𝑡 0.5 ∙ 𝐾 ∙ 𝑒 −𝑅𝑇

Where M: Migration
C0: Concentration of the migrant in the polymer
t: Time

16 Determination of Migration Rates for Certain Phthalates


K: Constant
T: Temperature
E: Activation energy
R: Gas constant

The constant K is a material constant. In this context, the constant depends on the formulary of soft
PVC. The same is the case for the activation energy.

In practice, the migration of substances from plastics is measured in contact experiments under
estimated worst-case scenarios, because this will give a higher safety factor in health exposure
calculations. Some methods for food contact materials and for pharmaceuticals are standardised
which makes comparison of results much more transparent. Other migration studies where
standardised methods are not used have to be set up according to the use of the plastic. This is the
case for most migration studies for consumer products.

Attempts have also been made to standardise experiments for determination of migration rates
from soft PVC from consumer products to artificial saliva and sweat, but the success is limited and
the correlation between the amount of phthalates in the products, the migration rates and in vivo
adult studies simulating children sucking and chewing on soft PVC products is not obvious.

Determination of Migration Rates for Certain Phthalates 17


2. Factors affecting migration
rates

2.1 Physical and chemical properties of the five phthalates


For each of the five phthalates an overview of some of their chemical and physical properties is
given, e.g., structure, molecular weight and solubility parameter, as these are parameters that could
influence the migration.

TABLE 7
OVERVIEW OF RELEVANT CHEMICAL AND PHYSICAL PROPERTIES OF DEHP

Substance Bis (2-ethylhexyl) phthalate (DEHP)

Structure

Molecular 390.56 g/mol


weight

CAS No. 117-81-7

Migration Boiling point: 385 °C at 1013 hPa, vapour pressure: 0.000034 Pa at 20 °C,
properties partition coefficient (log value) log Pow= 7.5 (Hansen & Nilsson, 2014).
δd=16.6 MPa0.5 (Wypych, 2015). Water solubility 3 µg/liter at 25 °C (Staples
et al., 1997)

18 Determination of Migration Rates for Certain Phthalates


TABLE 8
OVERVIEW OF RELEVANT CHEMICAL AND PHYSICAL PROPERTIES OF DINP

Substance Diisononyl phthalate (DINP)

Structure

Molecular weight 418.61 g/mol

CAS No. 68515-48-0/28553-12-0

Migration properties DINP is not a pure substance, but a complex mixture containing
mainly C9 – branched alcohol isomers. Boiling point 244 to 252
°C at 7 hPa, vapour pressure: 9·10-7 hPa at 25 °C, partition
coefficient (log value) log Pow= 6.9 at 25 °C (Hansen & Nilsson,
2014). δd=16.2 MPa0.5(Wypych, 2015), water solubility < 1
µg/liter at 25 °C (Staples, 1997)

TABLE 9
OVERVIEW OF RELEVANT CHEMICAL AND PHYSICAL PROPERTIES OF BBP

Substance Benzyl butyl phthalate (BBP)

Structure

Molecular 312.37 g/mol


weight

CAS No. 85-68-7

Migration Boiling point: 370°C at 10.10 hPa, vapour pressure: 0.00112 Pa at 20°C,
properties partition coefficient (log value) log Pow= 4.84 (Hansen & Nilsson, 2014).
δd=19.1 MPa0.5 (Wypych, 2015), water solubility 2700 µg /liter at 25 °C
(Staples, 1997)

Determination of Migration Rates for Certain Phthalates 19


TABLE 10
OVERVIEW OF RELEVANT CHEMICAL AND PHYSICAL PROPERTIES OF DBP

Substance Dibutyl phthalate (DBP)

Structure

Molecular 278.35 g/mol


weight

CAS No. 84-74-2

Migration Boiling point: 340°C at 10.013 hPa, vapour pressure: 9.7±3.3·10-5 Pa at 25


properties °C, partition coefficient (log value) log Pow: 4.57 at 20°C (Hansen & Nilsson,
2014). δd=17.8 MPa0.5 (Wypych, 2015), water solubility 11200µg/liter at 25
°C (Staples et al., 1997)

TABLE 11
OVERVIEW OF RELEVANT CHEMICAL AND PHYSICAL PROPERTIES OF DIBP

Substance Diisobutyl phthalate (DIBP)

Structure

Molecular 278.35 g/mol


weight

CAS No. 84-69-5

Migration Boiling point: 320 °C, vapour pressure: 0.01 Pa at 20 °C, partition coefficient
properties (log value) log Pow: 4.11 (Hansen & Nilsson, 2014). The solubility parameter
(δd) is unknown, but the value is estimated to be similar to DBP, water
solubility: 20000 µg/liter at 25 °C (Staples et al., 1997).

From the physical/chemical properties such as the solubility parameter and water solubility, the
migration rate will be different for the five phthalates. At the same concentration levels, the
migration rates for DBP and DIBP are expected to be the highest of the five phthalates. BBP is
expected to have migration rates between DBP and DIBP, and DEHP and DINP, which latter is
expected to have the lowest migration rates to artificial sweat and saliva.

20 Determination of Migration Rates for Certain Phthalates


2.2 Knowledge on formulary
In nearly all studies, the formulary of soft PVC is unknown. As the chemical substances in the
formulary can influence the migration rates of the phthalates significantly, e.g., by using plasticisers
in different concentrations and different chemical structure and mixtures, high filler content and
extender oils, there is no fixed migration rate for phthalates in soft PVC. If the material is foamed,
the number of closed and open cell structures will influence the migration because the cells will
contain air or blowing gases. In addition, the molecular weight distribution of the PVC raw material
and the amount of crystallites can influence the migration rates, as migration depends on the free
volume between the polymer PVC chains. The influence of the filler depends on amount and particle
size. Nanoparticular fillers can reduce the migration rates of plasticisers (Lirova, 2008).

The free volume is a measure of the internal space between the polymer chains. The higher the free
volume is, the better the polymer chains can move between each other. The addition of plasticisers
to rigid PVC lowers the glass transition temperature. In this way, they make the PVC more soft and
rubber-like by increasing the free volume between the PVC polymer chains. This is because they
force the chains from each other and in that way lowers the attraction between the PVC polymer
chains (the so-called Van der Waals forces).

2.3 History of samples


In most cases, the samples for determination of content of phthalates and for migration
measurements have been bought in supermarkets, toy shops etc. However, the history of the
samples is unknown regarding manufacture and shipment to the shops (temperature and humidity
during storage, packaging conditions) and storing before the customers purchase the product. All
these factors can affect the migration of the phthalates in an unpredictable way. Shashoua, 2001,
discusses factors affecting the migration and degradation of products made of soft PVC and stored
in museums for long time.

Generally phthalates can migrate to the surface of soft PVC during storage and transport,
phthalates that already have migrated to the surface of the products will contribute to the migration
rates determined in the migration tests, but that will not significantly change the content in the
article (Amberg Müller et al., 2010). In fact, the migration rate of the phthalates during exposure
under static conditions will be lower according to Fick´s law compared to dynamic conditions,
because the driving force is the difference in concentration between the outer part of the product
and the concentration in the borderline in contact with the simulant. For dynamic test, the
simulant at the surface will be exchanged with fresh simulant during the study, which will not be
the case in the static tests. However, the phthalates that already have migrated to the surface will
contribute to the concentration measured after exposure to the simulant, and therefore the
determined migration rate is expected to be higher - especially in dynamic migration studies as
explained above.

2.4 Sample preparation


The preparation of the sample before analysis can have a major influence on the results for the
migration step of the analysis. In some studies, the sample is washed/dipped in fresh simulant
before testing. Rinsing the surface with a detergent in water and rinsing with demineralised water
will make it possible to remove already migrated phthalate from the surface of the soft PVC product
before the migration test, and that will eliminate the problems with unknown prehistory mentioned
above. Cutting the PVC products for the migration test might result in new surfaces with a surface
structure that differs from the finished product.

2.5 Methods for migration analysis


Compared to the quantitative analysis of the specific phthalates in soft PVC, it is a challenge to
make consistent migration analysis for phthalates to artificial saliva and sweat. This is reflected in
the migration rates referenced in the open literature. The migration rates will be rather low in

Determination of Migration Rates for Certain Phthalates 21


comparison with the very short exposure time used in the analysis. This means that the result in
many cases will be that the concentration of phthalate is lower than the detection limit of the
method.

Major factors influencing the migration rate are:

 Formulary of the soft PVC


 The history of the article
 Homogeneity of the article
 Surface structure and volume of the article
 Sample preparation
 Temperature during contact with artificial saliva or sweat
 Static or dynamic test conditions
 Migration time
 Differences between the artificial saliva and human saliva
 Differences between artificial sweat and human sweat

A few parameters regarding the technical aspect of the extraction procedure also have to be
considered:

 Contamination of reagent solvents, utensils, glassware etc.


 Extraction yield in the concentration of phthalates by solvent extraction
 Selectivity of the chromatographic method of analysis and detection limit

2.5.1 Formulary, history and homogeneity of the article


As mentioned in chapter 2.2, the formulary of the soft PVC is usually unknown and so is the
prehistory and homogeneity. The parameters are only known in cases where reference materials of
soft PVC have been made.

2.5.2 Surface/volume/density of the article


The surface structure of the article might influence the migration rate as well as the volume/density.
If the article is foamed, the number of closed and open cells will influence the migration. For
foamed articles, the density will be low unless a filler has been added, like e.g., calcium carbonate.

2.5.3 Contamination of reagents, solvents, utensils, glassware etc.


It is common to specify that all laboratory equipment used for the analysis must be clean and
phthalate free. However, in laboratories the possibility still exists for contamination with phthalates
at low level because phthalates are also used for PVC hoses, in glue, etc. This is not problematic for
the quantitative analysis, as the concentrations used for plasticising purpose are much higher than
the levels of contamination from laboratory equipment. It can though be a problem when
measuring the migration, as the concentration of phthalates in the migration liquid is rather low.

2.5.4 Static and dynamic tests


It must be expected that the static tests give lower migration rates because the dynamic experiments
will remove already migrated phthalate from the sample surface.

In addition to the principle of dynamic testing, the shaking and stirring speed will influence the
migration rate in a complex way. The preparation of the sample for analysis will also influence the
migration. In most cases, a spherical or quadratic sample is removed from the article in various
ways, e.g., by using a hobby knife, by scissoring or by using a punching press or cork borer.

Loose particles of soft PVC that are liberated during the dynamic test can have a major influence on
the migration rate determined, as those particles will be extracted in the next step of the analysis

22 Determination of Migration Rates for Certain Phthalates


(solvent extraction) and result in significantly higher migration rates. For this reason the JRC
method describes the importance of avoiding loose particles in the sample preparation step.

2.5.5 Artificial saliva and sweat


Human saliva is a complex fluid, secreted by the major and minor saliva glands. A comparison
between natural saliva and very complex formulary is discussed including surface tension studies
(Preetha et al., 2005; Harvey et al., 2010; Callewaert et al., 2014).

As most studies for migration rates found in the literature have been carried out with artificial saliva
or sweat as simulants, examples of standardised formularies for these are given below.

TABLE 12
FORMULARY FOR ARTIFICIAL SALIVA ACCORDING TO SIMONEAU ET AL., 2001A

Compound mg/L

Magnesium chloride 166.7

Calcium chloride 147.0

Dipotassium hydrogen phosphate 753.1

Potassium carbonate 525.2

Sodium chloride 327.3

Potassium chloride 745.5

* The pH is adjusted to pH 6.8 by adding diluted hydrochloric acid.

TABLE 13
FORMULARY FOR ARTIFICIAL SALIVA ACCORDING TO BS 6684 (NOW WITHDRAWN)

Compound g/L

Sodium chloride 4.5

Potassium chloride 0.3

Sodium sulphate 0.3

Ammonium chloride 0.4

Urea 0.2

Lactic acid 3.0

* The pH is adjusted to 4.5 – 5.0 with 5 M sodium hydroxide in water.

Determination of Migration Rates for Certain Phthalates 23


TABLE 14
FORMULARY FOR ARTIFICIAL SWEAT ACCORDING TO DS/EN 1811:2011, 4TH EDITION, AND DS/EN ISO 105-E04:2013

Compound % w/w

Sodium chloride 0.5

Lactic acid 0.1

Carbamide 0.1

* The pH is adjusted to 6.50 by adding 1 and 0.1 M sodium hydroxide solution (in older formularies
0.1% ammonia solutions have been used instead).

TABLE 15
FORMULARY FOR ARTIFICIAL SWEAT ACCORDING TO EN-ISO 105-E04:2013

Chemical g/L

1-histidine-monohydrochloride-1- 0.5
hydrate

Sodium chloride 5

Sodium dihydrogen ortho phosphate 2.2


dihydrate

* The pH is adjusted to 5.5 with 0.1 M sodium hydroxide solution.

The simulants do not approach the properties of human saliva and human sweat. From the
composition, it is judged that they have been developed with the aim to study migration rates for
heavy metals like nickel, lead, cadmium and mercury. Complexity of human saliva, is discussed in
(Preetha, 2005) and human sweat it is discussed in (Harvey et al.,2010).

2.5.6 Extraction method and yield


When the sample has been exposed to artificial saliva or sweat, either statically or dynamically at
the test temperature and the chosen surface/volume ratio, the contact simulant is extracted by an
organic solvent. Examples are cyclohexane or dichloromethane (DCM) using a separatory funnel
and ensuring that phthalates adsorbed to the bottle used in the test also are transferred to the
funnel. The extraction step can be repeated to assure that the extraction yield is high.

The two phases are separated and the contact simulant (artificial saliva or sweat) is discarded. At
this stage, an internal standard is added to a known volume of the solvent phase for the calculation
of concentration in the chromatographic analysis.

The amount of phthalate to be analysed is very small and the solubility in water is very low, and
therefore the extraction step can be critical, as external contamination of phthalates from other
sources is possible, and as the phthalates might adhere to the surface of the glassware.

Solid phase micro extraction (SPME) was also used to concentrate the phthalates from the migrate
simulant after exposure.

24 Determination of Migration Rates for Certain Phthalates


2.5.7 Chromatographic analysis of contact simulant extracts
To quantify the specific phthalates it is estimated that the only reliable method of analysis is GC/MS
using a capillary column. The HPLC method, described in detail in the standard operating
procedure (SOP), in Simoneau et. al, 2001b, does not have sufficient selectivity (use of UV detector
at 225 nm) or resolving power (number of theoretical plates) to analyse migration extracts from soft
PVC articles with unknown formulary. The same SOP uses BBP as internal standard. BBP is part of
this study and cannot be used as internal standard for this reason alone. The risk of false positive is
expected to be larger in the HPLC method because the chosen UV detection wavelength is rather
unspecific. Only if the formulary is known, the HPLC method will be estimated to be valid.
Determination of the migrated phthalates by HPTLC (High Performance Thin layer
Chromatography) at least has the same drawback as HPLC because they are based on the same
chromatographic rules.

By using GC/MS analysis with capillary columns, a very efficient separation of the different
phthalates and phthalate isomers can be made even when the molecular structure is nearly iden-
tical. By using MS detection after separation, it is possible to avoid false positive. This can take place
by using the quantification ions in DS/CEN ISO /TS 16181:2011 and the column and
chromatographic parameters listed in this standard. A brief description of the method is
summarised below:
The extraction according to this method is carried out by using hexane/acetone 80%/20% for 1 h at
50 °C and transferring the extract to a volumetric flask after filtration or centrifugation. The
chromatographic column is specified in detail and so are the other GC parameters.

The primary MS target quantification ions are 149 m/z for DBP, BBP, DIBP and DEHP. For DINP
the target ion is 293 or 149 m/z, but supplementary quantification ions are suggested and used in
practice.

Determination of Migration Rates for Certain Phthalates 25


3. Results of the literature
search

3.1 Method used for the literature search


The literature search covered essential literature from 1998 to 2015, with focus on literature from
Denmark. In addition to studies from Denmark, a few other studies were included from the
Netherlands, Austria, Sweden, Germany, Great Britain, Turkey, Canada, Japan and the United
States. Besides the studies on migration rates, literature that discusses the results of the different
migration studies was also investigated.

The literature search focused on migration rates for the five phthalates (DEHP, DINP, DBP, DIBP
and BBP) in soft PVC to artificial sweat and artificial saliva and for in vivo tests when such studies
were available. The search took place in basic scientific journals as well as in reports from test and
research institutes. The results for migration rates from the literature search are listed in the
Appendix and tables are listed later in this chapter.

In the survey, standardised test methods for analysis of phthalates, sample preparation and
extraction methods were identified as well as standards for formulating artificial sweat and saliva.

A search on Google was conducted using the following terms: migration rates for phthalates,
migration rates for the individual five phthalates, analysis of phthalates, migration rates for
phthalates in consumer products, toys and childcare articles. The search terms have also been used
in the EU databases (ECHA, Rapex, Annex 15), the Danish EPA, The Federal Institute for Risk
Assessment (BfR) and the LOUS reports.

A collection of basic properties of the five phthalates has been updated as part of the literature
search. A list of the identified documents, reports, and scientific journals of relevance has been
compiled in the reference list.

3.2 Migration rates of the five phthalates


Overviews of the proposed migration rates according to the method the migration analysis has been
carried out appear in the tables below.

The analytical methods to determine the migration of phthalates are divided into three categories:
mild, medium and harsh conditions as seen in table 16. The mild conditions result generally in
lower migration rates compared with the in vivo adult migration rates for the simulation of
children’s sucking and chewing on soft PVC products.

TABLE 16
ANALYSIS METHODS DIVIDED INTO DIFFERENT CONDITIONS

Analysis method

Mild Static or dynamic conditions at 37±3°C (DK, A, TR, U.S.A.)

Medium Head over heels method at 60 rpm (NL)

Harsh Horizontal shaking at 300 rpm (J)

26 Determination of Migration Rates for Certain Phthalates


In Japan, and in the UK (Braybrook et al., 1998), a lot of effort has been used to get as high
migration rates as possible. This was done by using very rough dynamic mechanical influence, e.g.,
using centrifugal forces and high temperatures (for example the UK use 65 °C in some experiments)
in an attempt to obtain results in line with in vivo tests.

To our knowledge it is on a scientific base not possible to compare the conditions (chewing) of
adults with the chewing/mouthing of children, as the oral cavity (e.g. musculature) of a child’s
mouth is not fully developed. Therefore, the chewing force of children is expected to be weaker than
for adults. In addition, the stimulation of the saliva production by chewing might be different for
children compared with adults. It can be questioned if the results from the in vivo adult studies are
close to a realistic value for phthalate migration rates2 for children mouthing or chewing on
products.

Very different results for in vitro migration are obtained depending on how vigorous the applied
dynamic forces were. Therefore, it has been necessary to divide the proposed migration rates
according to the experimental set-up used in the countries that carried out the studies.

The results have been divided in minimum, mean and maximum values similar to Wormuth et al.,
2006. The mean is obtained by taking all the mean values from the studies in the three conditions.

All results are recorded as µg/cm2/h. If another unit has been used in literature, it has been
converted to this common unit by a calculation, which makes comparison between different
literature results much easier. The recalculations used the listed masses, surface areas and exposure
time from the references (if the experimental time was set to e.g. 16 hours, then the determined
migration rate was divided with 16 to convert the migration rate into the desired unit).

No migrations rates were found for BBP in the reviewed migration studies from the literature
search. BBP was analysed for and detected in some products (e.g., sandals in the Danish EPA report
no. 107, 2010 - Phthalates in plastic sandals), but the content of BBP was below the detection limit
in most quantitative characterisations and in all the migration studies. This is as expected, as their
most common use is for flooring and wallpaper. It is expected that the migration rate of BBP would
be similar or a little lower than DBP and DIBP due to the similar solubility parameter (δD) and
partition coefficient (Kow). Wormuth et al., 2006 and Wormuth, 2006b listed migration rates for
BBP (Average migration rate was 0.002 µg/cm2/min and 0.02 µg/cm2/min respectively), but it was
not possible to find the original reference with product information and analysis method.

The figures below show the migration rates of the remaining four phthalates as a function of
phthalate content.

2 Conferred with Professor Dorte Haubek, Aarhus School of Dentistry, Aarhus the 7th December 2015.

Determination of Migration Rates for Certain Phthalates 27


FIGURE 6
MIGRATION RATE AS A FUNCTION OF DEHP CONTENT (%W/W) FOR THE MILD CONDITIONS (LEFT GRAPH) AND
MEDIUM AND HARSH CONDITIONS (RIGHT GRAPH)

Medium
DEHP Mild DEHP
Harsh
4
Migrationrate [µg/cm2/h

Migration rate [µg/cm2/h]


120

3 100
80
2 60
40
1
20

0 0
0 20 40 60 0 20 40 60

Content [w/w%] Content [% w/w]

FIGURE 7
MIGRATION RATE AS A FUNCTION OF DINP CONTENT (%W/W) WITH MILD CONDITIONS (LEFT GRAPH) AND
MEDIUM AND HARSH CONDITIONS (RIGHT GRAPH)
Medium
DINP Mild DINP
Harsh
14 140
Migration rate [µg/cm2/h]
Migration rate [µg/cm2/h]

12 120
10 100
8 80
6 60
4 40
2 20
0 0
0 10 20 30 40 0 20 40 60
Content [% w/w] Content [% w/w]

FIGURE 8
MIGRATION RATE AS A FUNCTION OF DBP CONTENT (%W/W) WITH MILD CONTIDIONS (LEFT GRAPH) AND HARSH
CONDITIONS (RIGHT GRAPH)

DBP Mild DBP Harsh

0,7 160
Migrtionrate [µg/cm2/h]

Migrtionrate [µg/cm2/h]

0,6 140

0,5 120
100
0,4
80
0,3
60
0,2 40
0,1 20
0 0
0 10 20 30 40 0 5 10
Content [% w/w] Content [% w/w]

28 Determination of Migration Rates for Certain Phthalates


FIGURE 9
MIGRATION RATE AS A FUNCTION OF DIBP CONTENT (%W/W)

DIBP
7
Migrationrate [µg/cm2/h]

6
5
4
3
Mild
2
1
0
0 10 20 30 40
Content [% w/w]

The migration rates illustrated in the figures above have been divided into the mild, medium and
harsh analytical method conditions as explained above. In most cases it seems that very low
concentrations of phthalates results in relatively low migration rates, but there does not seem to be
a clear correlation between the migration rates and the content of the four phthalates. The results
have then been subdivided in minimum, mean and maximum values similar to Wormuth et al.,
2006. The mean is obtained by taking all the mean values from the studies in the three conditions.

TABLE 17
MIGRATION RATES FOR THE MILD ANALYTICAL METHOD CONDITIONS

Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 0.002 0.27±0.62 3.31

DINP 0.09 1.61±2.80 13.3

DBP 0.001 0.17±0.24 0.66

DIBP 0.04 0.77±1.39 5.80

TABLE 18
MIGRATION RATES FOR THE MEDIUM ANALYTICAL METHOD CONDITIONS

Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 0.04 10.7±7.99 31.3

DINP 1.5 13.3±6.44 29.1

DBP - - -

DIBP - - -

TABLE 19
MIGRATION RATES FOR THE HARSH ANALYTICAL METHOD CONDITIONS

Determination of Migration Rates for Certain Phthalates 29


Migration Rate from PVC (µg/cm2/h)

Phthalate Minimum Mean Maximum

DEHP 4.4 54.6±41.0 118

DINP 7.8 44.8±33.4 124.8

DBP 1.17 48.5±46.9 144.8

DIBP - - -

3.3 The analysis methods from the literature survey


The studied analysis methods had very different conditions e.g. temperature, exposure time,
static/dynamic test and different simulants.

Each subject is discussed further below, while looking into the differences in the method used for
the determination of migration.

3.3.1 Temperature and migration time


The Danish EPA studies and some of the international studies of phthalate migration rates for
consumer products were carried out at 37 °C or 40 °C as that is close to the human body
temperature. The migration time differs depending on “worst-case” exposure scenarios for the
products. This lead to migration times varying from 10 – 15 minutes up to 24 hours depending on
the products. In many cases that means that the amount of migrating phthalate is below the
detection limit of the analysis because the contact time is too low, for the phthalates to migrate e.g.,
0.5 h to 4 h.

Analysis of the migrate might be carried out according to DS/EN 71-11 for toys but the analysis of
phthalates is not part of the standard. The temperature of exposure is 20 °C according to DS/EN 71-
10 and the JRC method. This is different from most other migration studies where the temperature
is close to the body temperature (35 °C to 40 °C).

The reason for using 20 °C instead of 37 °C is judged to be for practical reasons, however some
studies using the JRC method perform the method at 37 °C.

It must be expected that migration rates will increase with temperature according to the rules for
migration.

3.3.2 The static and dynamic tests used in the analysis methods
In some of the migration studies, both static and dynamic test conditions were carried out. In
general, the dynamic tests in Denmark, Turkey, Austria and the U.S. are very mild using gentle
shaking or magnetic stirring, where static or dynamic test were conducted at 37 °C. The migration
rates are quite low compared to the tests carried out in the Netherlands and Japan. The
Netherlands use the Head over Heels method at 60 rpm, while Japan uses horizontal shaking at
300 rpm. In the UK, the experiments were carried out to obtain very high migration rates, e.g., by
increasing the temperature to 65 °C (Braybrook et al., 1998).

The following principles for dynamic methods were identified:


 Head over heels
 Horizontal shaking
 Vertical shaking
 Magnetic stirring

30 Determination of Migration Rates for Certain Phthalates


 Ultrasound
 Pneumatic piston
 In vivo chewing/sucking

Babich 1998 (Chen, 1998) conducted phthalate migration studies by using either shaking or
impaction for 6 h at 37 °C to compare in vitro and in vivo results. The impaction method used an
air driven piston, with a force of 0.91 kg, 2.7 kg or 5.4 kg, a piston sizes of 1.27 cm, 1.59 cm or 2.54
cm. The piston was active for 2 seconds following a period of 2 seconds without pressure. The
impaction method gave the best correlation with the in vivo measurements if the results were
multiplied by a factor of 39.5.

Fiala et al., 2000 and Steiner et al., 1998 have compared different agitation methods for the release
of DEHP and DINP into saliva simulant. The methods and their respective migration rates are
shown in Figure 10 and Figure 11
.

FIGURE 10
MIGRATION RATES OF DEHP WITH DIFFERENT TEST CONDITIONS (FIALA ET AL., 2000)

DEHP
2.64
µg/cm2/h

1.28
1.06 1.02

0.37
0.13 0.07 0.13 0.07 0.14

FIGURE 11
MIGRATION RATES OF DINP WITH DIFFERENT TEST CONDITIONS (FIALA ET AL., 2000)

Determination of Migration Rates for Certain Phthalates 31


DINP
13.3

8.33 8.75
µg/cm2/h

3.87
3.02

0.24 0.36

Static 3h shaking 3h ultrasonic 3h sucking 1h sucking 3h chewing 1h chewing 3h

Static conditions gave the lowest phthalate migration rate. Shaking did not significantly increase the
migration rate; however, by using ultrasonic extraction the migration rate increased 10-fold. The
average DEHP release using ultrasonic extraction was half the value compared to the average in
vivo release migration rates. The release of DINP using ultrasound extraction was comparable with
the in vivo release. Bouma et al., 2002, has compared the results from the studies of Fiala et al.
2000, and Steiner et al. 1998, with the head over heels method (HOH) method validated by
Toegepast Natuurwetenschappelijk Onderzoek (TNO - the Dutch Organisation for Applied Scientific
Research). The result was that the release of DINP was higher than in the in vivo release.

The Head over Heels (HOH) method is the preferred method for migration studies for toys in the
EU because many studies have been carried out to standardise this dynamic way of exposure
(Report to the U.S. Consumer Product Safety Commission, 2014). The method is described in
Simoneau et al., 2001a and in Simoneau et al, 2001b. The method has been developed with the aim
to be used for the determination of migration from toys. The standard EN 71-10 for toys also uses
the HOH extraction dynamic test for migration studies.

The extraction bottles for both methods have a volume of 250 ml and the lid has a PTFE lined
rubber septum. The HOH makes use of a bottle rotator capable of holding the extraction bottles in
an end-over-end motion at a constant speed. The distance from the centre of the rotating axis to the
centre of the flask will be approximately 150 mm. The rotator is rotated at 60+/-5 rpm for 60 +/-5
minutes. The preferred size of the sample is 10 cm2 surface and the amount of simulant 100 ml.
After exposure, the aqueous migrate solution in the bottle is filtered through a plug of glass wool.

3.3.3 Artificial saliva and sweat used in the literature


Human saliva is a complex fluid, secreted by the major and minor saliva glands. A comparison
between natural saliva and very complex formulary is discussed including surface tension studies
(Preetha et al., 2005; Harvey et al., 2010; Callewaert, 2014).

However, most migration studies for phthalate migration to artificial saliva and sweat simulants
utilise simpler formulations, probably due to reasons related to chemical analysis as the artificial
saliva is stable, and possible interference from substances found in human saliva is avoided.

The simulants do not approach the properties of human saliva and human sweat. From the
composition it is judged that they have been developed with the aim to study migration rates for
heavy metals like nickel, lead, cadmium and mercury. Complexity of human saliva, is discussed in
(Preetha et al., 2005) and human sweat it is discussed in (Harvey et al., 2010).

32 Determination of Migration Rates for Certain Phthalates


3.4 ECHA´s opinion and conclusions based on available literature
regarding DINP migration rates to artificial saliva
ECHA, 2013 has made an evaluation of new scientific evidence concerning DINP and DIDP
including migration rates for DINP to artificial saliva and in vivo adult saliva. The migration rates
for the other four phthalates were not evaluated in this report, with the exception of some
comparison with DEHP.

Most migration studies have been carried out with DINP as DINP is the phthalate found in most
toys and it has often been found in high concentrations (NICNAS, 2010).

The results discussed by ECHA are presented in the table below:

TABLE 20
MIGRATION RATES USED IN ASSESSMENT OF CHILDREN´S EXPOSURE TO DINP IN TOYS (ECHA, 2013)

Study/reference Rate Comments


µg/cm2/h

RIVM, 1998; Meuling et 10.8 Adult volunteer study: chew and spit, 10 cm2
al., 2000 disc. Mean levels of leaching for 3 objects,
8.28, 14.64 and 9.78 µg/cm2/h respectively
(overall mean 10.8 µg/cm2/h)

EC Risk Assessment (EC 53.4 Highest rate of leaching in the RIVM, 1998
2003 a) study

Sugita et al., 2003 9.24 +/- 5.68 Study in adult volunteers asked to suck or lick
specimens of PVC toys. Average rates for
individual toys ranged from 1.32 to 24.04
µg/cm2/h

US CPSC, 2002 7.0 In vitro rates of 6.0 – 66.6 µg/cm2/h with


mean of 24.6 µg/cm2/h determined for 41
children´s objects (head over heel method);
calibrated against chew and spit in vivo
measurements of adult volunteers (mean in
vivo: in vitro ratio 0.28)

Chap 2001 (Chen 1998 as 60 95% upper confidence bound from US CPSC
reported in Chap 2001) data.

As stated in ECHA, 2013: “that migration of phthalates depends on type of contact, time,
temperature, plasticiser concentration difference, plasticiser level, molecular weight and molecular
structure. In addition, another element that seems important when determining the migration rate
is the process conditions for PVC manufacturing. A relationship between the plasticiser’s content of
PVC and the migration of plasticisers from PVC cannot be established based on experimental
data. The likely reason for this is the multitude of factors influencing the migration from PVC in
combination with differences in experimental settings among the studies. Niino et al., 2003 a
reported high effects of especially rotation speed (a migration rate of ca. 20 µg/cm2/h at 200 rpm
versus ca. 150 µg/cm2/h at 400 rpm) and temperature (a migration rate of ca. 80 µg/cm2/h at 20
°C and ca. 170 µg/cm2/h at 40 °C)”.

Within the same experiment referred to above, higher percentages of DINP in general seemed to
have resulted in higher migration rates, although it should be noted that data reported in Chen,
1998 did not indicate a clear relation between phthalate content and in vitro migration rates

Determination of Migration Rates for Certain Phthalates 33


measured by means of impaction from 35 toys and childcare articles. Babich, 1998 has tabulated the
results from Chen, 1998. In Chen, 1998 migration rates for the in vivo test were in average 39.5
times higher. This is in conflict with the results of Niino, 2003 where the in vivo migration rate was
about four times lower than the in vitro results.

A more in-depth discussion in ECHA, 2013 from a report made by TNO (TNO, 2010) of the data for
migration rates of DINP to artificial saliva has led to the conclusion that the migration rate from
mouthing of toys will be an in vitro migration rate of 45 µg/cm2/h, measured for a plate with a
content of 40.7% w/w DINP and a typical in vivo estimate will be 14 µg/cm2/h. The latter value of
the migration rate is based on taking the mean of all the means from the in vivo studies. It is not
evident why the in vivo results are lower than the in vitro result, but it is very interesting that the
proposal for in vitro migration rates in this report are comparable with the in vivo results from
ECHA, 2013.

However ECHA, 2013 concludes also that it is not straightforward to give preference to the in vivo
data over the in vitro data as an estimate of the real-life migration during mouthing behaviour of
children. This is fully in agreement with our opinion based on our discussion regarding the
mouthing of children’s compared with adults.

ECHA, 2013 finds that the lack of standardisation of the in vivo methods and the high variability in
measurements is problematic. It is concluded that the in vivo data might not give a good
representation of the population of toys on the European marked. On the other hand, it is
mentioned that in vitro data might overestimate average real-life migration rates, and a lot of the
available in vitro data has not been carried out by the current European standard (EN 71-10). It
must be stressed that this standard is part of the three standards DS/EN 71-9, DS/EN 71-10 and
DS/EN 71-11, which are valid for the study of migration of organic substances from toys. However,
migration of phthalates is as already mentioned not covered by the standards.

ECHA, 2013 has also discussed the migration rates from sex toys, mainly based on Nilsson et al.,
2006, VWA, 2009 and Janssen and Bremmer, 2010. Nilsson et al., 2006 found the worst-case
migration rates for a vibrator with a content of 70.2% w/w DEHP run at maximum speed in contact
with artificial sweat adjusted to pH 4.5 equal to the vaginal pH level for healthy women for 1 h at 40
°C. The migration rate was 0.06 µg/cm2/h. By simulating the use of a water-based lubricant and an
oil-based lubricant, the migration rates increased to 0.4 µg/cm2/h and 54.8 µg/cm2/h. VWA 2009
found a rather high average migration rate of DINP (56.2 µg/cm2/h) from sex toys with a maximum
rate 224.4 µg/cm2/h. VWA, 2009 used the head over heels method for the migration in sweat.
Janssen and Bremmer, 2010 used maximum migration rates of 224 µg/cm2/h for DINP in sex toys
for calculations of exposure. They used the HOH method on isolated parts of the article and a
correction factor of 0.5 was used. ECHA, 2013 concludes that a typical value for the migration of
DINP from sex toys is 65 µg/cm2/h based on the merged data from VWA, 2009 and worst-case will
be 121 µg/cm2/h based on the 75th fractile from the same study.

In the reference US CPSC, 2002, the results of Chen, 1998 have been discussed. Chen, 1998
determined the migration rate into simulated saliva by using the HOH method from the Joint
Research Centre (Simoneau et al., 2001) for DEHP and DINP with the following results
(µg/cm2/min):

34 Determination of Migration Rates for Certain Phthalates


TABLE 21
MIGRATION RATES IN µG/CM2/MIN FOR TOYS MEASURED BY THE JRC DYNAMIC MIGRATION METHOD (HOH)
(CHEN, 1998)

DEHP DINP

N* 3 25

Mean 0.13 0.42

S.D. 0.06 0.28

Max. 0.20 1.11

*N=Number of products

3.5 Methodology for proposal of migration rates


From the literature study, it appears that no specific scientifically based true migration rates exist
for each of the five phthalates DEHP, DINP, BBP, DIBP and DBP and neither do true migration
rates based on in vivo migration studies. Too many factors affect the migration rates especially with
regard to the experimental set up both in the in vitro and the in vivo determination of migration
rates. Most of the literature considers the migration of DINP in detail; especially for the in vivo
migration studies DINP has been the “case story”, probably because it was found that DINP was the
most commonly used phthalate plasticiser in toys.

Due to lacking correlation between several migration studies for phthalates, it seems reasonable to
consider the model used by Wormuth et al., 2006, where the migration rates are divided into
minimum, mean and maximum migration rates based on the literature present at the time of
publication. In Wormuth et al., 2006, migration rates from studies carried out later than 2006 and
up to today were taken into consideration (see table 22). The listed migrations rates differ from
Wormuth, 2006b with a significant factor for DEHP, BBP and DBP, but are in similar range for
DINP.

TABLE 22
PHTHALATE MIGRATION RATES (WORMUTH ET AL., 2006)

Release Rate from PVC (µg/cm2/min)

Phthalate Minimum Mean Maximum Remarks

DEHP 0.000 0.050 0.236 Mechanical agitation using artificial saliva;


experiments with human volunteers

DINP 0.000 0.206 0.359 Mechanical agitation using artificial saliva;


experiments with human volunteers

BBP 0.000 0.002 0.004 Mechanical agitation using artificial saliva;


no maximum reported

DBP 0.000 0.001 0.002 Mechanical agitation using artificial saliva;


only samples with low DBP content
considered

It should be noted that the migration rates to sweat (skin contact) are expected to increase
dramatically if the skin is treated with suntan lotion or other skincare products with oil/fat
lubricants for DEHP or DINP (Danish EPA no. 77, 2006 and Danish EPA no. 107, 2010). Regarding
oral contact, it is expected that the migration rates of DEHP and DINP will increase dramatically

Determination of Migration Rates for Certain Phthalates 35


when babies lick products that contain phthalates after ingesting fat containing milk. For the more
water soluble phthalates BBP, DIBP and DBP the effect of treatment as stated above is expected to
be lower due to their more hydrophilic properties and that has been experimentally verified.

In some phthalate studies (LGC, 1999), the aim has been to obtain high migration rates that are
comparable with the migration rates obtained in in vivo studies. In (LGC, 1999), CSTEE has
requested a method capable of achieving a migration level for DINP to artificial saliva of 54.0
µg/cm2/h (based on a maximum migration value of 53.4 µg/cm2/h found in an in vivo study from
an actual toy – RIVM, 1998). However, the mean migration rates in RIVM, 1998 are in the order of
maximum 10 µg/cm2/h, which is close to the suggested migration rate in this report.

Higher migration rates can be obtained by increasing the dynamic force and/or temperature.

3.5.1 Dynamic force


When using high agitation speed, the migration increases due to a combination of the G-force
𝑅𝑃𝑀
𝐺 − 𝑓𝑜𝑟𝑐𝑒 = 1.12 ∙ 𝑟𝑎𝑑𝑖𝑢𝑠 ∙ ( ) ²) generated by the centrifugal rotation in the HOH method,
1000
which can drag the phthalates out of the PVC and a more efficient stirring will remove DEHP and
the other phthalates from the surface.

A calculation of the G-force (which the PVC sample is exposed to in the HOH method) has been
carried out based on 250 ml flasks, which have a distance of 150 mm from rotation axis to flask and
where a rotation of 60 revolutions per minute is used. Based on that the acceleration can be
4𝜋2 𝑟
calculated from the formula 𝑎 = where r is the radius (0.15 m) and t the time for one rotation (1
𝑡2
s) corresponding to 60 revolutions/min. From that formula, the acceleration is calculated to 5.9
m/s2 or 0.6 G. It can be calculated that by going from 60 rev/min. to 400 rev/min. the G force will
increase from 0.66 to 26.6, which is a very high force. That partly explains why very high migration
rates were found in some studies by Niino et al., 2002, at high revolutions.

In LGC, 1999, a combination of temperature and dynamic force was used to simulate in vivo
migration rates. The test was an exaggerated test at 65 °C with 10 stainless steel balls (12 mm Ø)
and it was dynamically tested in a horizontal linear/transvers shaking bath (with an amplitude of
movement of 38 mm). The agitation speed of 200 strokes/minute and the exposure time is 2 x 30
minutes exposure time for a disc with surface area of 10 cm2 and artificial saliva is used. After the
first 30 minutes, fresh saliva was added for the next 30-minute treatment, and the 2 x 50 ml
artificial saliva was combined for extraction with, e.g., DCM for chromatographic analysis. The
described in vitro method was used to achieve similar migration rates as found in vivo studies.
Therefore, the tables in the appendix with suggested migration rates for the phthalates have been
divided into three groups where the migration studies with extreme dynamic stress has been used,
and migration studies where less harsh exposure experiments have been used. This approach has
resulted in migration rates that depend on in which method the test was carried out from. No
attempt was made to consider the in vivo results as the” true” migration rates for reasons discussed
above.

36 Determination of Migration Rates for Certain Phthalates


3.5.2 Physical and chemical parameters
Besides the results from the literature regarding migration rates, the important physical and
chemical parameters in the table below will be considered especially by determining the mutual
migration rates for the five phthalates. The parameters stated earlier in Chapter 2.1 Physical and
chemical properties of the five phthalates are compiled in Table 23.

TABLE 23
IMPORTANT PARAMETERS TO CONSIDER REGARDING MIGRATION RATES OF PHTHALATES

Phthalate Mw, Delta, Log Water solubility


g/mol (Pow)
MPa0.5 25 °C., µg/l

DEHP 390.56 16.6 7.5 3

DINP 418.61 16.2 6.9 <1

BBP 312.37 19.1 4.84 2700

DBP 278.35 17.8 4.57 11200

DIBP 278.35 17.8 4.11 20000

Staples, 1997 has discussed different methods for the determination of the solubility of phthalates
in water. Especially for the phthalates like DEHP and DINP with long alkyl chains, many
experimental data appear confusing and result in too high values compared with the prediction of
theoretical models. By using a HOH-like technique (shake flask/centrifugation method) will result
in an increase in solubility for DEHP in water that is around 10-fold. By using the HOH-like method
for measurement of water solubility, colloidal emulsions of undissolved phthalates might be formed
and they are difficult to separate from the water phase.

As the water solubility of DEHP and DINP is very low (3 µg/l and < 1 µg/l at 25 °C), and as most
migration studies use 100 ml of simulant, the amount of dissolved phthalate in the water phase will
be 10 times less in mass because 100 ml is one tenth of 1 liter. Therefore, it seems reasonable to
conclude that in the migration studies where high dynamic and mechanical stress is applied, a
major part of the phthalates DEHP and DINP are present in the simulants as emulsions. By
increasing the temperature to 37 °C or even 65 °C, more of the migrated phthalates might be soluble
due to the higher temperature of exposure.

3.5.3 Temperature and simulants


As observed in studies by Niino et al., 2003, and Rose et al., 2012, the temperature can be used to
increase migration.

In Rose et al., 2012 a study was performed on migration of DEHP from infusion sets made of PVC
with DEHP. The study was performed at temperatures from 24°C, 32°C and 37°C and with
migration to 0.9% saline solution and to 3 different lipid-based infusates using 6-hour migration
periods. The study showed that a migration to saline solution could be detected only at 37 °C (425
µg) but not at lower temperatures.

When using lipid-based infusate, the migration increased with a factor of 1.7 to 6 when increasing
the temperature from 24 °C to 37 °C depending on simulant type/test conditions. This illustrates
that temperature and the extraction medium are important in order to obtain the realistic migration
rate.

Determination of Migration Rates for Certain Phthalates 37


For this reason, tests should ideally be carried out at temperatures close to body temperature and it
should be considered to develop other simulants than the presently used artificial saliva and sweat.
Saliva may contain fatty emulsions from ingestion of food, e.g., milk and vegetable fat and at
contact with suntan lotion and fat/oil-containing cosmetics the migration can increase several
orders from 5 – 1000 times.

For practical reasons it will be much easier to use the EN 71-10 method described for toys and with
water as simulant and then make further studies similar to the method used for infusion sets to get
a measure of the level of migration using the much more easy EN 71-10 method at 20°C and 1 h
exposure time and with pure water as simulant. Even though the body temperature is 37 °C, the
small difference in temperature will not affect the migration rate significantly, because the exposure
time is so short.

3.6 Migration rates proposed


Based on the literature search and the rules for migration it is obvious that one realistic migration
rate for each of the five phthalates in focus in this report: DINP, DEHP, BBP, DBP and DIBP cannot
be determined as the rates depend on the method used for the migration study.

As a lack of standard method makes a comparison between the different studies carried out it will
be a great step ahead if a common agreement regarding the future method for carrying out
migration studies can be made. The most convenient way to choose will be the method described in
EN 71-10 by using pure water as the simulant for both sweat and saliva. The most optimal way will
also be to carry out the migration step at 20 °C for 1 hour for practical reasons as recommended in
the standard instead of 37° C having in mind that migration rates will increase with temperature.

The head over heels method (HOH) is judged as the most documented method of all, but only for
the migration rates for DINP and DEHP to artificial saliva and is in our opinion the most realistic.
For this reason, the HOH method is recommended as the reference method for the determination of
migration rates for phthalates well knowing that realistic migration rates are difficult to determine
in in vitro or adult in vivo studies.

Compared with the mild methods based on static tests or dynamic tests using mild shaking or
magnetic stirring the migration rates for the HOH method will be higher.

When the suggested migration rates for the five phthalates are used for risk assessment purposes, a
higher migration rate will result in more conservative risk assessment and in higher consumer
protection against exposure to phthalates. The migration rates can therefore be used to indicate
whether a product containing one of the five phthalates will pose a risk. The harsh method used by
the Japanese seems far from reality by using dynamic test at 300 rpm and is judged to give too high
migration rates.

As the HOH method first of all has been documented for DINP and DEHP the migration rates for
the other phthalates have been determined by using a correction factor based on the mild migration
studies or/and taking the chemical/physical properties of the phthalates in consideration
(molecular weight, solubility in water, log Kow, vapour pressure and δD (solubility parameter)).

It seems reasonable to use a one-hour exposure as migration will be higher in the beginning of the
exposure and makes it possible to carry out more analysis than for longer exposure times.

By using pure water (e.g. MilliQ quality) it will be possible to use TOC (total organic carbon)
analysis for the evaluation of the total migration of organic substances from the soft PVC.

38 Determination of Migration Rates for Certain Phthalates


This method is already used as an important parameter for the approval of plastic and rubber in
contact with drinking water, it is very robust and have a low detection limit. It can be used directly
on the water phase without using extraction and chromatography due to the principle of analysis
(converting organic carbon to carbon dioxide and measuring the concentration of carbon dioxide by
infrared dispersive detection).

At present as far as the many studies for migration of phthalates have been carried out in very
different ways it shall be recommended to use the following migration rates for calculation of risk of
exposure to the phthalates until further evidence is available:

 Use the means of all the migration rates calculated from the medium dynamic experiments
carried out according to the HOH method at 60 rpm where results are available (DINP and
DEHP), since this is the most documented method for migration rates studies.
 Not to distinguish between migration rates to artificial sweat and saliva
 To argue why the mild migration studies are not taken into account by multiplying with
DIBP and DBP mild migration rates together with the ratio of the DEHP and DINP
migration rates in the medium dynamic studies and the DEHP and DINP in the results
from the HOH method (See calculations below).
 To use the same migration rate for DBP as for DIBP based on the multiplication proposed
below.
 To use a migration rate for BBP as the mean between the migration rates for DEHP, DINP,
DBP and DIBP calculated as proposed, due to the physical/chemical properties from the
five phthalates.
 To consider the possible use of cosmetic products like sun oil and other skin care products
or fats when making risk assessments.

The migration rates of DIBP and DBP are expected to be above both DEHP and DINP due to their
solubility in water. Therefore, to estimate an average migration rate, the factors from the mild
conditions are not used even though the migration rate for DIBP and DBP are then calculated as the
same. From this condition and the above recommendations, DIBP and DBP will be estimated to
have the following migration rates:

𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑑𝑖𝑢𝑚 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐸𝐻𝑃 𝑎𝑛𝑑 𝐷𝐼𝑁𝑃


Migration rate for DIBP =
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑙𝑑 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐸𝐻𝑃 𝑎𝑛𝑑 𝐷𝐼𝑁𝑃

10.7𝜇𝑔/𝑐𝑚2 /ℎ + 13.3𝜇𝑔/𝑐𝑚2 /ℎ
2 12𝜇𝑔/𝑐𝑚2 /ℎ
= 2 2 = = 12.77𝜇𝑔/𝑐𝑚2 /ℎ
0.27𝜇𝑔/𝑐𝑚 /ℎ + 1.61𝜇𝑔/𝑐𝑚 /ℎ 0.94 𝜇𝑔/𝑐𝑚2 /ℎ
2
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑑𝑖𝑢𝑚 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐸𝐻𝑃 𝑎𝑛𝑑 𝐷𝐼𝑁𝑃
Migration rate for DBP = = 12.77𝜇𝑔/𝑐𝑚2/ℎ
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑙𝑑 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐸𝐻𝑃 𝑎𝑛𝑑 𝐷𝐼𝑁𝑃

The migration rate of BBP, should be in between the four other phthalates and is calculated as the
average of these values:

𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑑𝑖𝑢𝑚 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐸𝐻𝑃 𝑎𝑛𝑑 𝐷𝐼𝑁𝑃+𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑑𝑖𝑢𝑚 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒𝑠 𝑜𝑓 𝐷𝐼𝐵𝑃 𝑎𝑛𝑑 𝐷𝐵𝑃
=
2

10.7 𝜇𝑔/𝑐𝑚2 /ℎ + 13.3 𝜇𝑔/𝑐𝑚2 /ℎ


+ 12.77 𝜇𝑔/𝑐𝑚2 /ℎ
= 2 = 12.39𝜇𝑔/𝑐𝑚2 /ℎ
2

Therefore, the migration rates for the five phthalates using the HOH method are estimated to:

Determination of Migration Rates for Certain Phthalates 39


TABLE 24
ESTIMATED MIGRATION RATES FOR THE FIVE PHTALATES

DEHP DINP DIBP DBP BBP

Migration rate (µg/cm2/h) 10 13 13 13 12

The migration rates for the five phthalates are all in the same range. But the results from Wormuth
et al. 2006 are rather different except for DINP. It would be expected from the chemical/physical
properties that the migration rates for DBP and BBP should be higher than DINP and that DEHP
should be at the same order as DINP and this is not the case. The true migration rates for DIBP and
DBP would most likely be higher than DINP and DEHP, but because the concentrations in most
cases are lower, the migration rates become similar. This could explain why the results are not
compatible with Wormuth et al., 2006, because there are low concentrations of the phthalates in
the products and these are most likely added as a processing aid before adding DEHP or DINP, but
still have a softening effect. In Wormuth et al., 2006 it is also stated that only samples with low
DIBP content are considered. According to Fick’s law the migration rate will depend on the
concentration level, therefore without knowing the phthalate content, it is difficult to compare the
listed migration rates in table 24 with the results found from Wormuth et al., 2006.

40 Determination of Migration Rates for Certain Phthalates


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Determination of Migration Rates for Certain Phthalates 41


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Determination of Migration Rates for Certain Phthalates 43


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44 Determination of Migration Rates for Certain Phthalates


5. Appendix

The migration rates found in the literature appear in the tables below. The migration rates are listed
according to each phthalate (in the order DEHP, DINP, DBP and DIBP) and with respect to the
migration rates for sweat and saliva. All results are recorded as µg/cm2/h. If another unit was used
in literature, it has been converted to this common unit by a calculation as that makes it much
easier to compare the different literature results.

5.1 DEHP

5.1.1 Migration to artificial sweat

TABLE 25
OVERVIEW OF MIGRATION STUDIES FOR DEHP IN SWEAT – ALL SAMPLES WERE ANALYSED USING GC-MS

Sample Content of Migration Migration Simulant Extraction/ Reference Country


name DEHP rate conditions dilution
(%w/w) (µg/cm2/h) solvent

Oil cloth 25.3 0.05 Static condition DS/EN ISO DCM Danish EPA DK
1.6 for 10 min at 105-E04 no. 109,
37±3°C. 2010

Oilcloth 1.8 13 0.09 Static condition DS/EN ISO DCM Danish EPA DK
for 1 hour at 105-E04 no. 109,
37±3°C. 2010

Balance 44.2 0.38 Static condition DS/EN ISO DCM Danish EPA DK
ball 1.14 for 1 hour at 105-E04 no. 109,
37±3°C. 2010

Swimming 25.8 0.11 Static condition DS/EN ISO DCM Danish EPA DK
pool 1.18 for 1 hour at 105-E04 no. 109,
37±3°C. 2010

Shower 25.1 0.06 Static condition DS/EN ISO DCM Danish EPA DK
curtain for 1 hour at 105-E04 no. 109,
1.31 37±3°C. 2010

Shower 29.6 0.08 Static condition DS/EN ISO DCM Danish EPA DK
curtain for 1 hour at 105-E04 no. 109,
1.39 37±3°C. 2010

Toilet bag 17.6 0.06 Static condition DS/EN ISO DCM Danish EPA DK
1.65 for 1 hour at 105-E04 no. 109,
37±3°C. 2010

Wrist 15 0.01 Static conditions DS/EN ISO THF Danish EPA DK


watch U10 for 24 hour at 105-E04 no. 139,
37±3°C. 2010

Sex toys 2 0.07 0.01 Static conditions DS/ISO DCM Danish EPA DK
for 1 hour at 12870:1997( no. 77, 2006

Determination of Migration Rates for Certain Phthalates 45


Sample Content of Migration Migration Simulant Extraction/ Reference Country
name DEHP rate conditions dilution
(%w/w) (µg/cm2/h) solvent

40°C. E). 1.
edition

Sex toys 8 70.2 0.06 Static conditions DS/ISO DCM Danish EPA DK
for 1 hour at 12870:1997( no. 77, 2006
40°C. E). 1.
edition

Sex toys 14 17.6 0.06 Static conditions DS/ISO DCM Danish EPA DK
for 1 hour at 12870:1997( no. 77, 2006
40°C. E). 1.
edition

Sex toys 15 20 0.05 Static conditions DS/ISO DCM Danish EPA DK


for 1 hour at 12870:1997( no. 77, 2006
40°C. E). 1.
edition

Plastic 2.2 0.01 Static condition DS/EN ISO DCM Danish EPA DK
sandal 1.1* for 16 hours at 105-E04 no. 107,
37±3°C. 2010

Plastic 0.002 0.005 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
5.2** 37±3°C. 2010

Plastic 30.2 0.011 Static condition DS/EN ISO DCM Danish EPA DK
sandal 6.1* for 16 hours at 105-E04 no. 107,
37±3°C. 2010

Plastic 14.8 0.004 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
8.1a* 37±3°C. 2010

Plastic 14.8 0.098 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
8.1b* 37±3°C with new 2010
simulant after 8
hours.

Plastic 14.8 0.006125 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 8 hours at 105-E04 no. 107,
8.1c* 37±3°C. 2010

Plastic 14.8 0.1782 Dynamic DS/EN ISO DCM Danish EPA DK


sandal condition for 16 105-E04 no. 107,
8.1d* hours at 37±3°C. 2010

Plastic 14.8 0.0952 Static condition DS/EN ISO DCM Danish EPA DK
sandal with sunscreen 105-E04 no. 107,
8.1e* for 16 hours at 2010
37±3°C.

Plastic 14.8 0.8214 Dynamic DS/EN ISO DCM Danish EPA DK


sandal condition with 105-E04 no. 107,
8.1f* sunscreen for 16 2010

46 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction/ Reference Country
name DEHP rate conditions dilution
(%w/w) (µg/cm2/h) solvent

hours at 37±3°C.

Plastic 17.1 0.005 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
8.2** 37±3°C. 2010

Plastic 46.1 0.019 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
12.1* 37±3°C. 2010

Plastic 0.03 0.06 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
13.2** 37±3°C. 2010

Plastic 24.5 0.006 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
17.1* 37±3°C. 2010

Plastic 11.1 0.00940 Static condition DS/EN ISO DCM Danish EPA DK
sandal 18.1 for 16 hours at 105-E04 no. 107,
– Middle of 37±3°C. 2010
the sole

Plastic 21 0.00401 Static condition DS/EN ISO DCM Danish EPA DK


sandal 18.2 for 16 hours at 105-E04 no. 107,
– The 37±3°C. 2010
outer part
of the sole

Plastic 1 0.1084 Static condition DS/EN ISO DCM Danish EPA DK


sandal for 16 hours at 105-E04 no. 107,
20.2** 37±3°C. 2010

Plastic 34.5 0.00608 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
26.1* 37±3°C. 2010

Plastic <LOD 0.00229 Static condition DS/EN ISO DCM Danish EPA DK
sandal 29.2 for 16 hours at 105-E04 no. 107,
– The 37±3°C. 2010
outer part
of the sole

Plastic 20.9 0.02216 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
37.2** 37±3°C. 2010

Plastic 25.8 0.04778 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
39.2** 37±3°C. 2010

Plastic 32.8 0.00510 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
43.1* 37±3°C. 2010

Plastic 46.2 0.01234 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,

Determination of Migration Rates for Certain Phthalates 47


Sample Content of Migration Migration Simulant Extraction/ Reference Country
name DEHP rate conditions dilution
(%w/w) (µg/cm2/h) solvent

44.1* 37±3°C. 2010

Plastic 10.5 0.04102 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
46.1* 37±3°C. 2010

Plastic 15.4 0.01379 Static condition DS/EN ISO DCM Danish EPA DK
sandal 46.2 for 16 hours at 105-E04 no. 107,
– The 37±3°C. 2010
outer part
of the sole

Plastic 0.37 0.003703 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
54.2** 37±3°C. 2010

Plastic 0.013 0.006125 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107,
55.1* 37±3°C. 2010

Toy 1 33.9 1.659 Static conditions DIN V BnBzO Özer and TR


in 2 hours for 53160-2 Gücer 2012
40°C.

Toy 3 37.9 3.314 Static conditions DIN V BnBzO Özer and TR


in 2 hours for 53160-2 Gücer 2012
40°C.
* Sole of the sandal, ** Strap of the sandal, DCM = Dichloromethane, THF = tetrahydrofuran, BnBzO = Benzoic acid benzyl ester

48 Determination of Migration Rates for Certain Phthalates


5.1.2 Migration to artificial saliva

TABLE 26
OVERVIEW OF MIGRATION STUDIES FOR DEHP IN SALIVA

Sample Content of Migration Migration Simulant Extraction Analysis Reference Country


name DEHP rate conditions /dilution method
(%w/w) (µg/cm2/h) solvent

Oilcloth 25.3 0.05 Static EU project DCM GC-MS Danish EPA DK


1.6 condition for 1 (Simoneau et no. 109,
hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Oilcloth 13 0.07 Static EU project DCM GC-MS Danish EPA DK


1.8 condition for 1 (Simoneau et no. 109,
hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Balance 44.2 0.24 Static EU project DCM GC-MS Danish EPA DK


ball 1.14 condition for 1 (Simoneau et no. 109,
hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Swimming 25.8 0.08 Static EU project DCM GC-MS Danish EPA DK


pool 1.18 condition for 1 (Simoneau et no. 109,
hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Shower 25.1 0.04 Static EU project DCM GC-MS Danish EPA DK


curtain condition for 1 (Simoneau et no. 109,
1.31 hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Shower 29.6 0.06 Static EU project DCM GC-MS Danish EPA DK


curtain condition for 1 (Simoneau et no. 109,
1.39 hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Toilet bag 17.6 0.08 Static EU project DCM GC-MS Danish EPA DK
1.65 condition for 1 (Simoneau et no. 109,
hour at 37±3°C al., 2001, EUR 2010
19826 EN)

Doll 3 3 1.86 Head over EU project Isooctane HPLC Bouma et al., NL


Heels method (Simoneau et 2002
al., 2001, EUR
19826 EN)

Doll 8 38 17.64 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Doll 10 39 31.32 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Doll 15 44 13.56 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Determination of Migration Rates for Certain Phthalates 49


Sample Content of Migration Migration Simulant Extraction Analysis Reference Country
name DEHP rate conditions /dilution method
(%w/w) (µg/cm2/h) solvent

Inflatable 37 7.38 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
furniture Heels method 2001, EUR 2002
19899 EN

Inflatable 41 9.84 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
furniture Heels method 2001, EUR 2002
19899 EN

Swimming 33 9.84 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
tool 2 Heels method 2001, EUR 2002
19899 EN

Swimming 36 10.50 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
tool 3 Heels method 2001, EUR 2002
19899 EN

Swimming 37 7.86 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
tool 4 Heels method 2001, EUR 2002
19899 EN

Swimming 37 10.86 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
tool 5 Heels method 2001, EUR 2002
19899 EN

Apron 7 3.48 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Ball 1 34 10.62 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Can 34 3.78 Head over Simoneau et al., Isooctane HPLC Bouma et al., NL
Heels method 2001, EUR 2002
19899 EN

Plate B 47.7 118 Horizontal BS 6684:1987 ACN HPLC Niino et al., J


shaking at 300 British 2003
rpm for 15 min Standard
at 35°C

Plate D 14.7 45.6 Horizontal BS 6684:1987 ACN HPLC Niino et al., J


shaking at 300 British 2003
rpm for 15 min Standard
at 35°C

Plate F 13.2 6.4 Horizontal BS 6684:1987 ACN HPLC Niino et al., J


shaking at 300 British 2003
rpm for 15 min Standard
at 35°C

Soft doll C 31.1 52.8 Horizontal BS 6684:1987 ACN HPLC Niino et al., J
shaking at 300 British 2003
rpm for 15 min Standard
at 35°C

Ball A in 18.5 69.6 Horizontal BS 6684:1987 ACN HPLC Niino et al., J

50 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction Analysis Reference Country
name DEHP rate conditions /dilution method
(%w/w) (µg/cm2/h) solvent

vitro shaking at 300 British 2003


rpm for 15 min Standard
at 35°C

Ball A in 18.5 4.4 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

Ball B 37.0 85.2 Horizontal BS 6684:1987 ACN HPLC Niino et al., J


shaking at 300 British 2003
rpm for 15 min Standard
at 35°C

PVC plate 32 0.13 Static BS 6684:1987 DCM HPTLC Fiala et al. A


A conditions at British 2000
37°C for 3 Standard
hours.

PVC plate 32 0.065 Static BS 6684:1987 DCM HPTLC Fiala et al. A


B conditions at British 2000
37°C for 6 Standard
hours.

PVC plate 32 0.13 Shaking at BS 6684:1987 DCM HPTLC Fiala et al. A


C 37°C for 3 British 2000
hours Standard

PVC plate 32 0.067 Shaking at BS 6684:1987 DCM HPTLC Fiala et al. A


D 37°C for 6 British 2000
hours Standard

PVC plate 32 0.14 Shaking at BS 6684:1987 DCM HPTLC Fiala et al. A


E 37°C for 3 British 2000
hours with Standard
solvent change

PVC plate 32 0.37 Glass beads at BS 6684:1987 DCM HPTLC Fiala et al. A
F 37°C for 3 British 2000
hours. Standard

PVC plate 32 1.06 Ultrasonic at BS 6684:1987 DCM HPTLC Fiala et al. A


G 37°C for 3 British 2000
hours Standard

PVC plate 32 1.28 Ultrasonic at BS 6684:1987 DCM HPTLC Fiala et al. A


H 37°C for 3 British 2000
hours with Standard
solvent change

PVC plate I 32 1.018 Ultrasonic at BS 6684:1987 DCM HPTLC Fiala et al. A


37°C for 6 British 2000
hours Standard

PVC plate 32 2.64 Sucking for 6 - DCM HPTLC Fiala et al. A

Determination of Migration Rates for Certain Phthalates 51


Sample Content of Migration Migration Simulant Extraction Analysis Reference Country
name DEHP rate conditions /dilution method
(%w/w) (µg/cm2/h) solvent

J in vivo hours 2000

DCM = Dichloromethane, THF = Tetrahydrofuran, ACN = Acetonitrile

5.2 DINP

5.2.1 Migration to artificial sweat

TABLE 27
OVERVIEW OF MIGRATION STUDIES FOR DINP IN SWEAT – THE SAMPLE WAS EXTRACTED WITH
DICHLOROMETHANE AND ANALYSED USING GC-MS

Sample Content of Migration Migration Simulant Reference Country


name DINP rate conditions
(%w/w) (µg/cm2/h)

Sex toys 2 >50 <500 Static conditions for Sweat: DS/ISO Danish EPA DK
one hour at 40°C 12870:1997(E). no. 77, 2006
1. edition

5.2.2 Migration to artificial saliva

TABLE 28
OVERVIEW OF MIGRATION STUDIES FOR DINP IN SALIVA – NO SIMULANT WAS LISTED IN THE BABICH 1998

Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country


name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Doll 1 29 11.28 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 2 30 12.66 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 3 32 13.32 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 4 33 18.54 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 5 37 17.28 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 6 37 16.92 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 7 37 15.36 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

52 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Doll 9 38 15.96 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 11 42 19.74 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 12 43 16.32 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 13 45 9.54 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 14 45 17.34 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Doll 15 48 13.56 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Animal 16 5.52 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 1 Heels method 2001, EUR 2002
19899 EN

Animal 27 4.2 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 2 Heels method 2001, EUR 2002
19899 EN

Animal 28 13.92 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 3 Heels method 2001, EUR 2002
19899 EN

Animal 34 13.08 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 4 Heels method 2001, EUR 2002
19899 EN

Bath toy 1 33 29.1 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Bath toy 2 36 15.6 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Bath toy 3 40 20.76 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Bath toy 4 42 27 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Teething 45 11.1 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL

Determination of Migration Rates for Certain Phthalates 53


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

ring Heels method 2001, EUR 2002


19899 EN

Inflatable 30 8.34 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Ball Heels method 2001, EUR 2002
19899 EN

Inflatable 34 7.08 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
cushion Heels method 2001, EUR 2002
19899 EN

Inflatable 31 7.2 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
cushion Heels method 2001, EUR 2002
19899 EN

Swimming 31 6.12 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
tool 1 Heels method 2001, EUR 2002
19899 EN

Key ring 39 4.5 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 2 Heels method 2001, EUR 2002
19899 EN

Key ring 44 14.28 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 3 Heels method 2001, EUR 2002
19899 EN

Key ring 45 12.18 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
figure 4 Heels method 2001, EUR 2002
19899 EN

Ball 2 35 22.14 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Rucksack 23 1.5 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Rucksack 27 4.68 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
Heels method 2001, EUR 2002
19899 EN

Standard 39 11.82 Head over Simoneau et al., Isooctane GC-MS Bouma et al. NL
disk Heels method 2001, EUR 2002
19899 EN

Plate A in 46.2 124.8 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
vitro shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Plate A in 46.2 32.4 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

54 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Plate D 14.4 42.8 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Plate E 14.1 8 Horizontal BS6684: 1987 ACN HPLC Niino et al., J


shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Rattle in 38 83.6 Horizontal BS6684: 1987 ACN HPLC Niino et al., J


vitro shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Rattle in 38 22.4 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

Teether in 38.9 51.6 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
vitro shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Teether in 38.9 12.8 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

Pacifier in 58.3 73.2 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
vitro shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Pacifier in 58.3 20 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

Toy food 31.1 46 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Soft doll A 16 29.6 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Soft doll B 29 83.6 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
shaking at 300 British Standard 2003

Determination of Migration Rates for Certain Phthalates 55


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

rpm for 15 min


at 35°C

Ball C in 25.6 33.6 Horizontal BS6684: 1987 ACN HPLC Niino et al., J
vitro shaking at 300 British Standard 2003
rpm for 15 min
at 35°C

Ball C in 25.6 7.8 Gently chewed - ACN HPLC Niino et al., J


vivo for 15 min. 2003
Repeated four
times with 5
min breaks.

Yellow 36 0.24 Static BS6684:1987 DCM HPTLC Fiala et al A


teether I conditions at British Standard 2000
37°C for 3
hours.

Yellow 36 0.363 Shaking at BS6684:1987 DCM HPTLC Fiala et al A


teether II 37°C for 3 British Standard 2000
hours

Yellow 36 3.87 Ultrasonic at BS6684:1987 DCM HPTLC Fiala et al A


teether III 37°C for 3 British Standard 2000
hours

Yellow 36 8.33 Sucking 1 hour BS6684:1987 DCM HPTLC Fiala et al A


teether IV British Standard 2000

Yellow 36 3.02 Sucking 3 BS6684:1987 DCM HPTLC Fiala et al A


teether V hours British Standard 2000

Yellow 36 13.3 Chewing 1 hour BS6684:1987 DCM HPTLC Fiala et al A


teether VI British Standard 2000

Yellow 36 8.75 Chewing 3 BS6684:1987 DCM HPTLC Fiala et al A


teether VII hours. British Standard 2000

Toy ball B 25.5 7.8 Rotary shaker - ACN HPLC Niino et al J


in vivo at 300 rpm in 2002
an incubator at
35°C for 15
min.

Toy book 27.5 0.255 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-2 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 36.6 1.027 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-3 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

56 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Toy Tiger 48.1 1.045 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-5 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy 43.7 2.700 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
Dolphin 37 °C. phosphate 1998
1-6 Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 1-7 30.0 0.264 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 43.3 0.582 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-8 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 33.5 0.436 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-9 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 54.4 0.445 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-10 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Corner 44.0 1.382 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
Pads 1-11 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy Food 51.0 1.964 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
1-14 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy duck 40.8 0.327 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-1 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Determination of Migration Rates for Certain Phthalates 57


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Toy duck 42.7 4.400 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-2 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 50.3 0.355 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-3 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy fish 37.0 0.591 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-4 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy 36.1 1.264 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
treehouse 37 °C. phosphate 1998
2-5 Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Squeeze 32.6 1.209 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
toy 2-7 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Soother 30.2 0.136 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-8 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 25.6 0.145 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-9 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Teether 19.3 0.273 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-10 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy book 17.5 0.127 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-11 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

58 Determination of Migration Rates for Certain Phthalates


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Bath toy 15.1 0.091 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-12 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy turtle 35.4 0.336 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-13 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy bear 19.9 0.300 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-14 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Spoon 2-15 35.2 0.436 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Spoons 34.3 0.827 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
2-16 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Ball 3-1 41.2 0.536 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy bear 41.2 0.409 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
3-2 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy 3-3 27.1 0.264 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Toy block 43.0 0.500 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
3-4 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Determination of Migration Rates for Certain Phthalates 59


Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country
name DINP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Toy car 42.7 0.218 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
3-5 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

Squeeze 52.5 0.264 Temperature = Dulbecco’s Not available GC-MS Babich, M U.S.A.
toy 3-6 37 °C. phosphate 1998
Impacted by a buffered saline
pneumatic with 0.16 %
piston. mucin

THF = Tetrahydrofuran, ACN = Acetonitrile, DCM = Dichloromethane

60 Determination of Migration Rates for Certain Phthalates


5.3 DBP

5.3.1 Migration to artificial sweat

TABLE 29
OVERVIEW OF MIGRATION STUDIES FOR DBP IN SWEAT – ALL SAMPLES WERE ANALYSED USING GC-MS

Sample Content of Migration Migration Simulant Extraction/ Reference Country


name DBP (%w/w) rate conditions dilution
(µg/cm2/h) solvent

Plastic 22.9 0.42 Static condition DS/EN ISO DCM Danish EPA DK
sandal 1.1* for 16 hours at 105-E04 no. 107, 2010
37±3°C

Plastic 26.6 0.66 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107, 2010
5.2** 37±3°C

Plastic 1*10-4 0.009 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107, 2010
8.1b* 37±3°C, with
new simulant
after 8 hours.

Plastic 1*10-4 0.015 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 8 hours at 105-E04 no. 107, 2010
8.1c* 37±3°C.

Plastic 1*10-4 0.021 Dynamic DS/EN ISO DCM Danish EPA DK


sandal condition for 16 105-E04 no. 107, 2010
8.1d* hours at 37±3°C.

Plastic 1*10-4 0.0145 Static condition DS/EN ISO DCM Danish EPA DK
sandal with sunscreen 105-E04 no. 107, 2010
8.1e* for 16 hours at
37±3°C.

Plastic 1*10-4 0.0164 Dynamic DS/EN ISO DCM Danish EPA DK


sandal condition with 105-E04 no. 107, 2010
8.1f* sunscreen for 16
hours at 37±3°C.

Plastic 8 0.222 Static condition DS/EN ISO DCM Danish EPA DK


sandal for 16 hours at 105-E04 no. 107, 2010
8.2** 37±3°C.

Plastic 34 0.630 Static condition DS/EN ISO DCM Danish EPA DK


sandal for 16 hours at 105-E04 no. 107, 2010
13.2** 37±3°C.

Plastic 0.9 0.0168 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107, 2010
17.1* 37±3°C.

Plastic 0.2 0.00465 Static condition DS/EN ISO DCM Danish EPA DK
sandal 18.1 for 16 hours at 105-E04 no. 107, 2010
– Middle of 37±3°C.
sole

Plastic 0.08 0.00100 Static condition DS/EN ISO DCM Danish EPA DK

Determination of Migration Rates for Certain Phthalates 61


Sample Content of Migration Migration Simulant Extraction/ Reference Country
name DBP (%w/w) rate conditions dilution
(µg/cm2/h) solvent

sandal 18.2 for 16 hours at 105-E04 no. 107, 2010


– Outer 37±3°C.
part of sole

Plastic 17.8 0.4365 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107, 2010
20.2** 37±3°C.

Plastic 1.2 0.02813 Static condition DS/EN ISO DCM Danish EPA DK
sandal for 16 hours at 105-E04 no. 107, 2010
38.2** 37±3°C.

Plastic 0.29 0.001563 Static condition DS/EN ISO DCM Danish EPA DK
sandal 46.1 for 16 hours at 105-E04 no. 107, 2010
– Middle 37±3°C.
part of sole

* Sole of the sandal, ** Strap of the sandal, DCM = Dichloromethane

62 Determination of Migration Rates for Certain Phthalates


5.3.2 Migration to artificial saliva

TABLE 30
OVERVIEW OF MIGRATION STUDIES FOR DBP IN SALIVA – ALL SAMPLES WERE EXTRACTED WITH ACETONITRILE
AND ANALYSED USING HPLC

Sample Content of Migration Migration Simulant Reference Country


name DBP rate conditions
(%w/w) (µg/cm2/h)

Plate C 47.1 144.8 Horizontal shaking BS6684: 1987 Niino et al., J


at 300 rpm for 15 British 2003
min at 35°C Standard

Plate D 13.5 34.8 Horizontal shaking BS6684: 1987 Niino et al., J


at 300 rpm for 15 British 2003
min at 35°C Standard

Plate G 12.9 34.8 Horizontal shaking BS6684: 1987 Niino et al., J


at 300 rpm for 15 British 2003
min at 35°C Standard

Ball A In 10 58 Horizontal shaking BS6684: 1987 Niino et al., J


vitro at 300 rpm for 15 British 2003
min at 35°C Standard

Ball A in 10 1.2 Gently chewed for - Niino et al., J


vivo 15 min. Repeated 2003
four times with 5
min breaks.

Ball B 22 79.2 Horizontal shaking BS6684: 1987 Niino et al., J


at 300 rpm for 15 British 2003
min at 35°C Standard

Toy ball 10 3.39 Gently chewed for BS6684: 1987 Niino et al J


A in vitro 15 min. Repeated British 2001
four times with 5 Standard
min breaks.

Toy ball 10 1.17 Gently chewed for - Niino et al J


A in vivo 15 min. Repeated 2001
four times with 5
min breaks.

Determination of Migration Rates for Certain Phthalates 63


5.4 DIBP

5.4.1 Migration to artificial sweat

TABLE 31
OVERVIEW OF MIGRATION STUDIES FOR DIBP IN SWEAT

Sample Content Migration Migration Simulant Extraction/ Analysis Reference Country


name of DiBP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Wrist watch 7 0.037 Static conditions DS/EN ISO THF GC/MS Danish EPA DK
U06 under stirring 105-E04 with no. 139, 2015
for 24 hour at SPME
37±3°C.

Plastic 6.3 0.19 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 1.1* for 16 hours at 105-E04 no. 107, 2010
37±3°C.

Plastic 21.2 0.29 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 8.1a* for 16 hours at 105-E04 no. 107, 2010
37±3°C.

Plastic 21.2 0.32 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals for 16 hours at 105-E04 no. 107, 2010
8.1b* 37±3°C, with
new simulant
after 8 hours.

Plastic 21.2 0.49 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 8.1c* for 8 hours at 105-E04 no. 107, 2010
37±3°C.

Plastic 21.2 0.47 Dynamic DS/EN ISO DCM GC-MS Danish EPA DK
sandals condition for 16 105-E04 no. 107, 2010
8.1d* hours at 37±3°C.

Plastic 21 .2 0.97 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 8.1e* with sunscreen 105-E04 no. 107, 2010
for 16 hours at
37±3°C.

Plastic 21.2 1.12 Dynamic DS/EN ISO DCM GC-MS Danish EPA DK
sandals 8.1f* condition with 105-E04 no. 107, 2010
sunscreen for 16
hours at 37±3°C.

Plastic 7.4 0.30 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
8.2** 37±3°C.

Plastic 6.6 0.16 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
17.1* 37±3°C.

Plastic 2.2 0.14 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 18.1 for 16 hours at 105-E04 no. 107, 2010
- Middle of 37±3°C.
sole

64 Determination of Migration Rates for Certain Phthalates


Sample Content Migration Migration Simulant Extraction/ Analysis Reference Country
name of DiBP rate conditions dilution method
(%w/w) (µg/cm2/h) solvent

Plastic 11.7 0.24 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
18.2 The 37±3°C.
outer sole

Plastic 5.3 0.21 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
20.2** 37±3°C.

Plastic 1.6 0.13 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
29.2** 37±3°C.

Plastic 12.1 0.47 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
37.2** 37±3°C.

Plastic 12.1 0.40 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
38.2** 37±3°C.

Plastic 2.2 0.07 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
46.1* 37±3°C.

Plastic 3.9 0.10 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals - for 16 hours at 105-E04 no. 107, 2010
46.2 The 37±3°C.
outer sole

Plastic 3.3 0.49 Static condition DS/EN ISO DCM GC-MS Danish EPA DK
sandals 55.1* for 16 hours at 105-E04 no. 107, 2010
37±3°C. pH 5.5

Training ball 35.4 5.80 Static condition Simoneau et DCM GC-MS Danish EPA DK
1.24 for 1 hour at al., 2001, no. 109, 2010
37±3°C EUR 19826
EN

* Sole of the sandal, ** Strap of the sandal, DCM = Dichloromethane

Determination of Migration Rates for Certain Phthalates 65


5.4.2 Migration to artificial saliva

TABLE 32
OVERVIEW OF MIGRATION STUDIES FOR DIBP IN SALIVA

Sample Content of Migration Migration Simulant Extraction/ Analysis Reference Country


name DiBP (%w/w) rate conditions dilution method
(µg/cm2/h) solvent

Training 34.5 3.70 Static Simoneau et DCM GC-MS Danish EPA DK


ball 1.24 condition for al, 2001, EUR no. 109, 2010
1 hour at 19826 EN
37±3°C

Training 36.5 5.80 Static Simoneau et DCM GC-MS Danish EPA DK


ball condition for al, 2001, EUR no. 109, 2010
1 hour at 19826 EN
37±3°C

DCM = Dichloromethane

66 Determination of Migration Rates for Certain Phthalates


Determination of Migration Rates for Certain Phthalates
The purpose of the report is to suggest migration rates for the phthalates DEHP, DINP, BBP, DBP and
DIBP in soft PVC. The suggested migration rates will be based on numerous migration studies from the
accessible literature. The background to varying migration rates reported in the literature will be
investigated, discussed and evaluated. One of the major factors on the migration rate is the way the
migration analysis is carried out. Therefore, very different results were obtained depending on how
vigorous the applied dynamic forces were. Due to that major factor, it has been necessary to divide the
proposed migration rates according to the experimental set-up used. The analytical methods to
determine the migration of phthalates are therefore divided into three categories: mild, medium and
harsh conditions. The mild conditions result generally in lower migration rates compared with the in
vivo adult migration rates for the simulation of children’s sucking and chewing on soft PVC products.
The head over heels method (HOH) is judged as the most documented method of all, mostly for the
migration rates for DINP to artificial saliva, but also a few for DEHP. The HOH method seems to be the
most realistic method, since the given product is rotated once per second, which resembles how a child
will chew on a toy. For this reason and because the other methods are very different in their approach,
the HOH method is recommended as the reference method for the determination of migration rates for
phthalates well knowing that realistic migration rates are difficult to determine in in vitro or adult in vivo
studies. Calculations have been made in order to estimate migration rates for the five phthalates. The
basis is the HOH method, since this method seems to give the most realistic migration rates. The
estimated migration rates are quite close to each other (between 10 and 13 µg/cm2/h). The migration
rates for DIBP and DBP should in theory be higher than the migration rates for DINP and DEHP if the
content of the phthalates in the products are similar. The reason for the similar migration rates
estimated is that the concentrations of DIBP and DBP in most cases are lower than the concentration of
DEHP and DINP in the products. Even though results indicate that there is no correlation between the
content and migration, very low contents of phthalates are expected to give relatively lower migration
rates.

The Danish Environmental


Protection Agency
Strandgade 29
DK-1401 Copenhagen K

www.mst.dk

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