Notes

Bull. Korean Chem. Soc. 2012, Vol. 33, No. 10 3485

http://dx.doi.org/10.5012/bkcs.2012.33.10.3485

Optimization of Solvent for the Determination of Polybrominated Diphenyl

Ethers in High-Impact Polystyrene by GC/ECD
Dalho Kim,* Seungjin Park, Yongwook Choi, and Sung Kwang Lee
Center for Analytical Chemistry, Korea Research Institute of Standards and Science, Daejeon 305-340, Korea
*
E-mail: dhkim@kriss.re.kr

Department of Environmental Health Science, Jeonju University, Jeonju 560-759, Korea

Department of Chemistry, Hannam University, Daejeon 305-811, Korea

Received November 17, 2011, Accepted July 16, 2012
Key Words : Flame retardants, High impact polystyrene, Extraction efficiency, Certified reference material
(CRM), Solubility parameter

Polybrominated diphenyl ethers (PBDEs) are common

flame retardants that are used in a wide variety of products
such as computer casing and carpet.1 These chemicals
accumulate in both the environment and the human body.2
Recent findings indicate that exposure to low concentrations
of these chemicals may damage the nervous and reproductive systems. Recently, the European Union banned PBDE
compounds through the European Directive on Waste Electrical and Electronic Equipment (WEEE) and the European
Directive on the Restriction of the Use of Certain Hazardous
Substances in Electrical and Electronic Equipment (RoHS).3,4
These laws state that products should not contain PBDEs in
amounts above the limit of regulation and that products
containing PBDEs should be recycled.
High impact polystyrene (HIPS) is an important material
in housings and various parts of electronic devices.5 In order
to manage WEEE- and RoHS-related regulation of electronic waste, it is important to develop a reliable analytical
method for PBDEs in plastics, including optimization of
extraction.6 Recently, PBDEs were extracted from solid
environmental samples by soxhlet extraction, ultrasonic extraction, and accelerated solvent extraction; the typical solvents used are toluene, dichloromethane, and combinations of
hexane and acetone, dichloromethane and hexane, and npropanol and hexane.2 To extract PBDEs from polymers,
similar techniques have been used, together with organic
solvents such as methanol, n-propanol,1 toluene,7,8 isopropanol,9 iso-octane,10 and a combination of hexane and
acetone,11 toluene and tetrahydrofuran (THF)12 or toluene
and n-propanol.7 However, only Altwaiq et al. focused on
examining the extraction efficiencies of deca-BDE from
plastic matrices.7 The yield of an extraction is depend on
several factors, including the interactions among analytes,
solvents, and matrix in the extraction system. Our current
knowledge of the optimum conditions for extraction is incomplete. More study is required to select efficient solvents
to extract PBDEs from important matrices such as HIPS.
To address these issues, we performed an optimization
study to determine the solvent that would maximize extraction of PBDEs from HIPS resin for chromatographic

analysis. We prepared plastic samples, analyzed the sample

extracts by GC/ECD, and examined the efficiency of various
organic solvents for the extraction of PBDEs from the HIPS.
Analytical method was verified using a certified reference
material (CRM).
Experimental Section
Chemicals and Standard Materials. Octa-PBDE technical
mixture (octa bromo diphenyl oxide mix, FR-1208) was
product of the Dead Sea Bromine Co. (Beer Sheva,Israel).
PCB 153 (ChemService, West Chester, PA, USA) was used
as an internal standard. PBDE standard solutions (BDE 190,
196, 197, 198, 204, 207, and 208) were purchased from
AccuStandard (New Haven, CT, USA). The HIPS base
material was product of the BASF Company Ltd. Korea
(Polystyrol 476L, Pellet, Seoul, Republic of Korea), and
calcium stearate was purchased from the Shin Won Chemical
Co. Ltd. (HI-TECA, Siheung, Republic of Korea). Organic
solvents (methoxy ethanol, acetone, hexane, toluene, tetrahydrofuran (THF), 1-propanol, and dichloromethane) were
purchased from Burdick & Jackson (Muskegon, MI, USA).
Instruments. A Hewlett-Packard GC (HP-6890, Palo
Alto, CA, USA) and DB-5MS (crosslinked 5% phenyl methyl
silicone, 30 m 320 m 0.25 m) was used. Helium was
used as a carrier gas at a flow-rate of 2 mL/min. In the oncolumn mode, 1 L of sample was injected at 200 oC. An
ECD detector was used at 250 C, and for a makeup flow,
nitrogen gas was used at 60 mL/min. Oven temperature was
programmed as follows; The initial temperature of 90 C
was maintained for 5 min and then increased at a rate of 10
C/min to 320 C and maintained for 18 min. A cryogenic
grinding mill (SamplePrep 6750, SPEX, Middlesex, HA7
IBQ, UK) was used to grind the plastic samples.
Sample Preparation. To prepare a master batch sample,
1 mm sized preground HIPS (Polystyrol 476L), calcium stearate,
and the octa-PBDE technical mixture were premixed in a
tumbler mixer at room temperature for 20 min and then
extruded at 190 C. The HIPS sample was prepared by extrusion of the mixture of master batch sample and additional

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Bull. Korean Chem. Soc. 2012, Vol. 33, No. 10

HIPS (Polystyrol 476L) at 190 C.

Extraction and Clean-Up. Each sample was ground to a
size of 0.1-0.3 mm under cooling with liquid nitrogen.
Ground sample (0.25 g) was weighed in 50-mL centrifuge
tubes (polypropylene, disposable), and PCB-153 solution
was added as an internal standard. The sample was dissolved
using 12 mL of an appropriate solvent by ultrasonication for
15 min and shaking for 5 min. After dissolution, 15 mL
methanol was added into the sample solution to precipitate
the HIPS and then passed through a disposable syringe filter.
Each filtrate was collected in a new 50 mL centrifuge tube
and evaporated until dry at 40 C. The residue was then
reconstituted with 20 mL toluene.
Results and Discussion
Because a HIPS sample was dissolved (completely or
partly) in all the solvents, it was extracted by dissolution
with a solvent and precipitation with methanol. Figure 1
represents the efficiencies of various solvents for extracting
PBDEs from HIPS. We selected these solvents because they
are known as adequate solvents for PBDEs in various
matrices.2,5,7-9,11 The extraction efficiency of each solvent is
presented as the normalized total peak area of PBDEs based
on the highest total peak area (see Fig. 1). Toluene, the
combination of toluene and THF (1:1), and dichloromethane
yielded higher extraction efficiencies. The other solvents,
such as acetone/n-hexane (1:1), and toluene/n-propanol (1:1)
yielded approximately 20-25% lower extraction efficiencies
than toluene, toluene/THF (1:1) and dichloromethane.
These results can be explained by the solubility parameters of the compounds. The solubility parameter was used
to predict the physicochemical properties such as solubility
of a material. It is the sum of the forces (van der Waals

Notes

interactions, covalent bonds, hydrogen bonds and ionic

bonds) that hold the material intact. The total force of the
various interactions can be divided into partial solubility
parameters, i.e., dispersion (d), polar (p) and hydrogen
bonding (h). The partial solubility parameters can be calculated using the group contribution methods of Hoftizer and
Van Krevelens method and the total solubility parameter
(t), also called the three-dimensional solubility parameter,
of a compound can be calculated as follows.13
t = (d2 + p2 + h2)0.5
In addition, the difference of the solubility parameters
() can be used to predict the mutual solubility between
solute and solvent and can be calculated as follows (refers to
page 219 of the reference 13).
= [(d,S1-d,S2)2 + (p,S1-p,S2)2 + (h,S1-h,S2)2]0.5
where S1 and S2 are corresponding to partial solubility
parameter of each compounds (i.e. solvent-solute). In general,
a solute tends to be well dissolved in a solvent when the
solubility parameter components of solute and solvent have
similar values (i.e. when have small value) 13
Table 1 lists the experimental solubility parameter and its
components of several solvents, mixtures and polystyrene in
order of increasing polarity.14 We calculated the solubility
Table 1. Solubility parameter components of several solvents and
polystyrene14
t

14.9
16.4
18.2
18.4
19.1
19.5
19.9
20.0
20.2
24.6
29.6
48.0

14.9
15.2
18.0
17.4
19.02
16.8
15.5
17.0
18.2
16.0
15.1
12.2

0.0
5.2
1.4
3.6
1.1
5.7
10.4
4.1
6.3
6.8
12.3
22.8

0.0
3.5
2.0
5.0
0.0
8.0
7.0
9.7
6.1
17.4
22.3
40.4

Solvents or polymer
Hexane
Acetone/Hexane (1:1)
Toluene
Toluene/THF (1:1)
Polystyrene
THF
Acetone
Toluene/1-Propanol (1:1)
Dichloromethane
1-Propanol
Methanol
Water

Unit: MPa0.5 or (J/cm3)0.5, solubility parameter t = (d2 + p2 + h2)0.5

where d, p, and h represent dispersion force, polar and hydrogen
bonding components of the solubility parameter respectively.

Table 2. Solubility parameter components for several selected

congeners of PBDEs obtained by Hoftyer-Van Krevelen method

Figure 1. Extraction efficiencies of various organic solvents for

PBDEs in HIPS samples. 1, acetone/hexane (1:1); 2, toluene; 3,
toluene/THF (1:1); 4, toluene/1-propanol (1:1); 5, dichloromethane.
The extraction efficiency of each solvent is normalized based on
the result of toluene/THF.

PBDE
Congeners

t a

d a

pa

ha

Vb

Hexa
Hepta
Octa
Nona
Deca
Average

28.3
29.3
30.3
31.2
31.9
30.2

27.9
29.0
30.0
30.9
31.7
29.9

2.02
1.92
1.83
1.75
1.67
1.83

3.76
3.66
3.58
3.49
3.42
3.58

212.6
223.6
234.6
245.6
256.6
234.6

t = (d2 + p2 + h2)0.5. aunit: MPa0.5. bmolar volume, cm3/mol

Notes

Bull. Korean Chem. Soc. 2012, Vol. 33, No. 10

Table 3. Solubility parameter differences of PBDEs/solvent and

Polystyrene/solvent systems
Solvent
Acetone/Hexane (1:1)
Toluene
Toluene/THF (1:1)
Toluene/1-Propanol (1:1)
Dichloromethane

PBDEs-solventa
15.1
12.0
12.7
14.5
12.8

polystyrene-solvent
6.6
2.3
5.8
10.4
8.1

Unit: MPa0.5, Solubility parameter difference = [(d,S1-d,S2)2 + (p,S1p,S2)2 + (h,S1-h,S2)2]0.5 Refers to page 219 of the reference 13.
a
Average solubility parameter from hexa to deca-PBDE congeners was
used to calculate Solvent-PBDEs.

parameter components of PBDEs by Hoftizer and Van

Krevelens method,13 by adding the contributions from all
functional groups (see Table 2) because the experimental
data of PBDEs is not reported in literature. Table 3 lists the
solubility parameter difference for PBDEs/solvent (PBDEs13
solvent) and polystyrene/solvent systems (polystyrene-solvent).
Based on the solubility parameter differences, we selected
the toluene/THF (1:1) mixtures as an optimum extracting
solvent by relative comparison of the solubility parameter
differences (see Table 3), which correspondingly shows
higher extracting efficiency for PBDEs (see Fig. 1). According to the result of experiment (Fig. 1) and solubility parameter difference (Table 3), dichloromethane also can be
used as an optimal extraction solvent in this study but it was
not selected because it was volatile and carcinogenic. On the
other hand, toluene shows the lowest solubility parameter
difference with PBDEs, it also shows the lowest values with
polystyrene (see Table 3) which means it can similarly dissolve polystyrene. By this reason, polystyrene can be
remained in the final sample solution partly and can reduce
life of the column. Therefore, it was not selected as an
optimal extraction solvent.
To verify the extraction and GC/ECD method, KRISS
CRM (113-03-001, high impact polystyrene) was analyzed.
For this experiment, toluene/THF (1:1) was selected as the
optimal extraction solvent for PBDEs in HIPS and ten CRM
sample were independently prepared and analyzed by GC/
ECD. As presented in Figure 2, the GC/ECD chromatogram
of a sample prepared from the CRM shows the peak of each
PBDEs and internal standard are separated adequately. In
Table 4, the results of this experiment are presented and

3487

Table 4. Measurement results and certified values of PBDEs in

KRISS CRM
Certified
valuee
mg/kg

Congener
group

Peak
codea

BDE
Nob

Resultsc
mg/kg

Calibrantsd

Hexa-BDE

Hx1
Hx2
Hx3

154
153
-

10 1
79 5
4.0 0.4

BDE-154 11.4 0.8

BDE-154
BDE-154
-

Hepta-BDE

Hp1
Hp2
Hp3
Hp4
Hp5
Hp6

183
190

4.0 0.3
3.0 0.2
440 20
61
22 2
14 1

BDE-183
BDE-183
BDE-183
BDE-183
BDE-183
BDE-183

456 24
-

Octa-BDE

O1
O2
O3
O4

13 1
197, 204 246 13
203, 198 72 4
196
95 5

BDE-203
BDE-203
BDE-203
BDE-203

61 f
-

Nona-BDE

N1
N2
N3

208
207
206

4.0 0.3
227 14
16 1

BDE-206
BDE-206
BDE-206 17.3 2.6

Deca-BDE

209

18 2

BDE-209 20.0 2.4

Total

1272 58

Refers to GC-ECD chromatogram. PBDE congeners are numbered

according to IUPAC scheme. cTen independent samples were measured
by GC/ECD. dThe individual calibrants of PBDEs were prepared by
gravimetry using high purity materials. eFor certification, gas chromatography and isotope dilution mass spectrometry was used. finformation
value

compared with the certified value of the KRISS CRM. In

this experiment, to determine each PBDE, the individual
standard solutions of PBDE prepared by gravimetry using
high purity neat compound were used. At present, the high
purity compounds are not available for all isomers of
PBDEs. Therefore, to determine some PBDEs, their high
purity standard compounds are not available, the representative high purity standard in the same congener group
was used. For example, to determine BDE-153 the standard
solution of BDE-154 prepared by gravimetrically using high
purity BDE-154 was used. As presented in Table 2, the
analytical results of CRM by GC/ECD were comparable
with the certified values of CRM.
Conclusions

Figure 2. GC/ECD Chromatogram of the HIPS CRM KRISS

113-03-001 (regarding identity of each peak, refers to Table 4).

We examined the efficiencies of five combinations of

organic solvents for extracting PBDEs in HIPS samples
using shaking and ultrasonic extraction. Extraction with
toluene/THF (1:1), toluene or dichloromethane yielded high
extraction efficiencies for HIPS samples. The results demonstrate that the solvent used to extract PBDEs should be
selected based on the properties of the plastic, and a suitable
solvent can be selected by considering the solubility parameter of the target compound, plastic matrix and solvents.
Under the optimized solvent condition, entire method was

3488

Bull. Korean Chem. Soc. 2012, Vol. 33, No. 10

validated using KRISS CRM (113-03-001).

Acknowledgments. This work was supported by the
Korea Research Institute of Standard and Science (KRISS)
under the project Establishing Measurement Standards for
Food and Environmental Analysis, grant 12011026.
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