th

8 International Conference on Environmental Science and Technology

Lemnos island, Greece, 8 10 September 2003

SOLID-PHASE MICROEXTRACTION TO DETERMINE THE MIGRATION OF

PHTHALATES FROM PLASTIC WARE TO DRINKING WATER
K. PERDIKEA, E. PSILLAKIS, and N. KALOGERAKIS
Technical University of Crete, Department of Environmental Engineering,
Polytechnioupolis, 73100 Chania, Greece
E-mail: epsilaki@mred.tuc.gr
EXTENDED ABSTRACT
Phthalate esters are widely used as additives in the manufacture of plastics improving their
softness and flexibility. As these compounds are not chemically bound to the plastics, they
can easily penetrate these materials and migrate into the food or water that comes into direct
contact. The presence of phthalates in drinking water is usually in the low g/L contamination
level due to their hydrophobic nature. Today, phthalate esters are included in the priority lists
of pollutants in several countries and are being questioned worldwide because of their
potential toxicity to humans and the environment.
Solid Phase Microextraction (SPME) coupled to Gas Chromatography was used for the
determination of phthalate esters in water samples introducing thus a fast and solventless
analytical method enabling detection of these compounds in the low g/L concentration
levels. The major advantage of SPME over other preconcentration techniques was that it
minimized the risk of secondary contamination during sample preparation, a major parameter
to consider during phthalate contamination.
This paper investigates the extent of phthalates migration from several disposable plastic
materials into drinking water. The plastic materials investigated included plastic shakers used
for the preparation of iced coffee, plastic cups and plastic straws. The scope of the present
work was to investigate for the first time the effect of temperature on phthalate migration
establishing thus the safety of these materials when used with hot beverages as well as
demonstrating the importance of storage and transfer conditions of plastic materials
containing drinking water.
Overall, the results revealed that significant quantities of phthalates are expected to be
present in drinking water samples coming into direct contact with disposable plastic items at
elevated temperatures. The contamination level is higher when a prolonged exposure to
such temperatures is applied. Therefore, it is strongly advisable to control temperature during
the transfer, storage and/or handling of these materials.
Key words: SPME, phthalate esters, drinking water, water analysis

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1. INTRODUCTION
Dialkyl phthalate esters (phthalates) are widely used as plasticizers in the manufacture of
polyvinyl chloride to improve flexibility softness, workability and general handling properties.
The physical rather than chemical incorporation of phthalates in the polymeric matrix ensures
that they are widespread contaminants. Penetration of phthalates into the ecosystem or in
wastewater effluents occurs during the production phase and via leaching and volatilisation
from plastic products during their usage and/or after disposal. Furthermore, phthalates can
easily escape from plastic materials and migrate into the food, water or beverages coming
into direct contact with the packaging material [1]. The presence of phthalates in such
products depends on the initial concentration of phthalates in the packaging material,
contamination during production, as well as transfer and storage conditions [1].
Today, phthalates are included in the priority lists of pollutants in several countries and are
being questioned worldwide because of their potential toxicity to human health (in particular
on liver, kidney and reproductive system) and the environment. Some of them are known
teratogens when administrated repeatedly at low doses and their hepatocarcinogenic and
estrogenic activity has been recently documented. The most commonly occurring phthalates
are di-2-ethylhexyl phthalate (DEHP), di-n-butyl phthalate (DBP) and butylbenzyl phthalate
(BBP) [2,3,14]. In the 80s, the US Environmental Protection Agency (US EPA) and other
countries classified the commonly occurring phthalates as priority pollutants and
recommended 6 g/L as the maximum contamination level (MCL) for DEHP in water
systems and suggested close monitoring of all phthalate contaminants for concentrations
above 0.6 g/L [4].
Phthalates contamination is usually in the low g/L level due to their hydrophobic nature.
Various pre-concentration techniques, such as Liquid-Liquid Extraction (LLE) and SolidPhase Extraction (SPE), are commonly used to determine low phthalate concentrations in
aqueous samples [5,6]. The main disadvantage of these techniques is that apart form being
expensive, time-consuming and labour intensive, they typically result in secondary
contamination during sample preparation due to the presence of phthalates in many
laboratory products [7,8]. In this context the development of new fast and sensitive analytical
methods minimising the risk of phthalate contamination during sample treatment is of
paramount importance.
Solid-Phase Microextraction (SPME), introduced in 1990 by Arthur and Pawliszyn, is a fast,
simple and solventless sample preconcentration method [9]. The commercially available
SPME fibre consists of a thin polymeric-coated fused-silica fibre, fitted in a special syringetype holder for protection and sampling. During SPME sampling analytes partition by
adsorption or absorption (depending on the fibre type) from the solution to the stationary
phase and are concentrated. After sampling for a well-defined period of time, the fibre is
withdrawn and transferred to the heated injection port of a gas-chromatograph (GC) or to a
modified high-performance liquid-phase (HPLC) rheodyne valve [8]. SPME has gained the
attention of many research groups around the world and over the last decade, it has been
applied to the determination of a large variety of volatile and semi-volatile analytes, in several
types of environmental matrices [8,10]. Recently, the combination of SPME with GC enabled
detection of phthalates at low g/L contamination levels in water samples, minimising the risk
of secondary contamination, a major parameter to consider during phthalates trace analysis
[10,11].

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The aim of the present studies is to monitor and evaluate phthalates migration from several
disposable plastic materials into drinking water. The plastic materials investigated here
included: plastic shakers used for the preparation of iced coffee, plastic cups and plastic
straws. For the first time the effect of temperature on phthalate migration for these plastic
items was investigated establishing the safety of these materials when used with hot
beverages as well as demonstrating the importance of storage and transfer conditions of
plastic materials containing drinking water.
2. MATERIALS AND METHODS
2.1. Chemicals
Standard methanolic stock solutions containing 2000 mg/L of each target phthalate, namely:
dimethyl phthalate (DMP), diethyl phthalate (DEP), DBP, BBP, DEHP and di-n-octyl
phthalate (DOP) were purchased from Supelco (Bellefonte, PA, USA). A methanol solution of
benzyl benzoate (99+ %, Sigma-Aldrich Chemie GmbH) was used as the internal standard.
Working standard solutions of 50 mg/L were prepared weekly in methanol. Stock and
working standard solutions were stored at 4C. Aqueous solutions were prepared daily by
diluting the working standard solution in deionized water. Deionized water used for sample
preparation was prepared on a water purification system (EASYpureRF) supplied by
Barnstead/ Thermolyne. All solvents were pesticide-grade and were obtained from Merck
KgaA (Darmstadt, Germany).
2.2. Disposable plastic ware
All disposable plastic items examined here were purchased from a local supermarket. Two
brands of coffee shakers were investigated. Brand A was made of polystyrene (PS) and did
not contain water in its original packaging. Evaluation of phthalate migration for this particular
brand was achieved by adding 200 mL of deionized water each time. Brand B was made of
polypropylene (PP) and was vended with water in the plastic shaker. Disposable plastic cups
and straws made of PP were also examined.
2.3. Sample preparation and SPME procedure
For extraction, a 5 mL water sample was placed each time in 7-mL clear glass vial, equipped
with a glass-coated mini-impeller and fitted only with aluminium foil and screw caps with hole,
all purchased from Supelco (Bellefonte, PA, USA). Each morning standard solutions of all
target analytes were extracted by using SPME in order to ensure consistency. For all
quantification experiments, the aqueous solutions were spiked prior to extraction with the
exact amount of the internal standard solution. SPME was performed using a manual 65-m
polydimethylsiloxane-divinylbenzene (PDMS-DVB) SPME fibre and a SPME fibre holder
assembly all purchased from Supelco. The fibre was conditioned in the hot injector of a GC
device, before its first usage, according to the manufacturers recommendations. The SPME
fibre holder assembly was then clamped at a fixed location above the glass vial containing
the stirred (1000 rpm) sample solution. The SPME fibre was then exposed to the aqueous
phase and after sampling for 45 min the fibre was retracted and transferred to the heated
injection port of the GC-FID where it was left for 5 min.
2.4. GC-FID Analyses
Phthalates were analysed using a Shimadzu GC-17A (Ver. 3) Gas Chromatograph-Flame
Ionization Detector system. Injections were performed in the splitless mode at 280C with the
spilt closed for 5 min (solvent delay time). Helium was used as a carrier gas at a flow-rate of

700

1.2 mL/min. The Thermogreen LB-2 septa (Supelco, Sigma-Aldrich Chemie GmbH) were
pre-drilled. Analyte separation was performed on a 30m0.25mm, 0.25m SPB-1701
capillary column (Agilent Technologies). The column oven was initially set at 60C and then
programmed to 300C at a rate of 10C/min, where it was held for 11 min.
3. RESULTS AND DISCUSSION
3.1. Practical considerations during SPME/GC-FID and methods performance
To minimise the effect of secondary contamination associated with the analysis of trace
quantities of phthalates a number of measures were taken. All glassware and accessories
used in the experiments were washed several times with Suprasolv quality organic solvents
[13]. A glass-coated mini-impeller was used as a stirrer and aluminium foil replaced Teflon
septa. Furthermore, the thick protector needle of the SPME fibre irreversibly damaged the
thermo-resistant Thermogreen LB-2 septa used in the GC instrument. Such damages
typically resulted in carrier gas leaks, extraneous peaks and phthalate contamination due to
small polymer septa pieces introduced into the inlet liner of the GC injector. Pre-drilling the
septa prior to using them and replacing them on a daily basis avoided such damages [14].
Between runs a clean-up procedure for the SPME fibre eliminated the possibility of analyte
carry-over between analyses, a major drawback of SPME during phthalates analysis.
Accordingly, after desorption, the SPME fibre was immersed in a stirred solvent solution for 5
min and was subsequently transferred to the heated injection port (280C) of another GC
until the next extraction [15]. Moreover, blanks were run periodically during experiments to
confirm the absence of contaminants [11]. Despite the measures taken, GC-FID analysis of
deionized water, revealed the presence of phthalates in deionised water. It was assumed
that this background contamination originated from the GC septum or from water purification
system used for producing deionised water [12].
Calibration was performed by extracting water samples spiked in the concentration range
from 25 to 0.5 g/L for most target analytes. A very good linear correlation coefficient (r2) was
found for most phthalates (r2 > 0.9955), except for BBP and DEHP (r2 = 0.9724 and 0.9498
respectively). Repeatability expressed as the relative standard deviation (RSD) of five
consecutive replicates ranged between 4% and 10%. The limits of detection (LODs) were
determined according to published guidelines by comparing the signal-to-noise (S/N) ratio of
the lowest detectable concentration to a S/N ratio of three [9]. They were found in the lowppb level ranging between 0.03 and 0.4 g/L. Under the present experimental conditions
detection of trace quantities of DOP was not possible.
3.2. Analyses of drinking water coming into contact with plastic materials
A series of experiments were carried-out in which the effect of elevated temperatures on the
quality of drinking water coming into direct contact with plastic ware was investigated.
In the first series of experiments the effect of temperature on phthalate migration was
investigated for two brands of plastic shakers used for the preparation of iced coffee. These
series of experiments attempted to reproduce the high temperatures commonly found in
Greece especially during the summer. For the purpose of the present studies both shakers
containing 200 mL of water were sealed and left in the oven at 40C for several days. The
results on phthalates concentrations are summarized on Table 1. It should be mentioned

701

here that Brand A does not contain any water in its original packaging and as such deionised
water had to be added. Thus, Day 0 in the case of Brand A corresponds to the background
phthalate contamination originating from the deionised water. Brand B on the other hand is
vended with water in its original packaging. Day 0 in this case represents the initial phthalate
contamination. It should be mentioned here that the company producing Brand B imposes
storage of this product in refrigerators at all selling points. As such the initial phthalate
contamination most likely corresponds to contamination during the production phase. In all
cases nq stands for not quantified and denotes the presence of phthalates in
concentrations that could not be quantified at levels below the limits of quantification (0.5
g/L) but still greater than the limits of detection. This means that their presence in the
examined water samples could be confirmed but not quantified. Overall, the results revealed
that prolonged exposure of these plastic products on elevated temperatures facilitates
phthalates migration and results in phthalate-contamination at levels of significant concern.
Overall, Brand B yielded lower phthalate contamination than Brand A, despite the fact that it
remained at 40C for a much longer period of time. This observation reflects the lower risk
rank attributed to PP when compared to PS in the pyramid of plastics.
Table 1: The effect of temperature (40C) on drinking water quality coming into contact with
plastic coffee shakers
Brand A plastic shaker (PS)

Brand B plastic shaker (PP)

Analyte

Day 0
(g/L)

Day 1
(g/L)

Day 2
(g/L)

Day 12
(g/L)

Day 0
(g/L)

Day 3
(g/L)

Day 6
(g/L)

Day 7
(g/L)

Day 42
(g/L)

DMP
DEP
DBP
BBP
DEHP

nq
nq
nq
nq

2.84
2.63
2.70
nq
0.67

3.21
2.95
3.17
nq
0.68

2.09
5.13
6.22
nq
0.74

nq
nq

nq
nq

nq
0.55
1.38

0.74
0.73
1.67

1.61
1.65
2.03

nq

In another series of experiments the two brands of coffee shakers were left outdoors,
exposed to real conditions such as heat and sunlight. The temperature during exposure of
Brand A ranged from 12 to 28C and for Brand B from 18 to 36C. The results are
summarised in Table 2.
Table 2: Drinking water quality coming into contact with plastic coffee shakers exposed at
ambient conditions
Brand A plastic shaker (PS)

Brand B plastic shaker (PP)

Analyte

Day 0
(g/L)

Day 2
(g/L)

Day 37
(g/L)

Day 0
(g/L)

Day 61
(g/L)

DMP
DEP
DBP
BBP
DEHP

nq
nq

nq

1.65
1.31
0.90

1.08
1.4
1.70

nq

nq
nq

0.93
nq
2.22

nq

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Once again the results revealed that exposure of these plastic materials under elevated
temperatures facilitate phthalates migration into water. As expected phthalate migration is
not as extensive as it was in the first series of experiments, most certainly because the
plastic shakers were not continuously exposed to elevated temperatures. Brand A results in
a more significant phthalate contamination when compared to Brand B. Both series of
experiments stress-out the importance of temperature control during transfer, storage and
handling of these products.
Furthermore, the degree of phthalate migration originating from disposable plastic cups and
straws was investigated. Because these items may come into direct contact with hot
beverages, the experimental conditions had to be changed. Accordingly hot tap water was
added in a plastic cup for 30 min. Portion of the tap water was analyzed prior heating it and it
was assumed that the presence of phthalates, if any, was below the limits of detection of the
analytical method used here. The results (Table 3) revealed that under the present
experimental conditions, only DBP could be extracted. In the case of the straws, each item
destined for investigation was completely immersed in 100 mL hot tap water and was left
there for 30 min. In both brands of straws (Brand 1 and 2) DMP and DBP were found present
in the samples. However in the case of Brand 2 the DMP concentration was of significant
concern. Overall, the results suggested that the above mentioned plastic items are safe to
use only with cold drinks.
Table 3: Results on phthalate concentration originating from plastic cups and straws after a
30 min exposure with hot tap water.
Plastic Straws (g/L)
Plastic Cup (g/L)
Analyte
Brand 1
Brand 2
DMP
DEP
DBP
BBP
DEHP

4.

nq

nq

nq

2.84
nq
nq

CONCLUSIONS

Overall, significant quantities of phthalates are expected to be present in drinking water

samples coming into direct contact with several disposable plastic items at elevated
temperatures. The contamination level is higher when a prolonged exposure to such
temperatures is applied. Therefore, it is strongly advisable to control temperature during the
transfer, storage and/or handling of these materials.
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