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Procedia Environmental Sciences 16 (2012) 552 – 559

The 7th International Conference on Waste Management and Technology

Brominated flame retardants (BFRs) in waste electrical and

electronic equipment (WEEE) plastics and printed circuit
boards (PCBs)
Yuan Chena, Jinhui Lia,*, Lieqiang Chenb, Shusheng Chenc, Weihua Diaoc
a
School of Environment, Tsinghua University, Beijing, 100084, China
State Key Joint Laboratory of Environment Simulation and Pollution Control (SKLESPC)
b
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640
c
Dongjiang Environmental Company Limited, Shenzhen, 518057, China

Abstract

Two kinds of BFRs in three WEEE plastics(cell phone shells, computer housings and TV housings) and PCBs were
detected with GC/MS. The results showed the plastics used as mobile phone shells had no BFRs. TBBPA was only
found in computer housings. Among PBDEs, congeners of heptabromodiphenyl ether, octabromodiphenyl ether and
nonabromodiphenyl ether were frequent ones, and detected in both TV housings and computer housings. But the
contents of N9BDE were lower than the other two, only 180 mg/kg and 5.3 mg/kg in computer housings and TV
housings respectively, while pentabromodiphenyl ether and hexabromodiphenyl ether were determined in PCBs.

© 2012
© 2012 Selection
The Authors. Published
and/or by Elsevier
peer-review B.V.
under responsibility of Basel Convention Coordinating Centre for Asia and the Pacific
Selection and/or peer-review under responsibility of BaselofConvention
and National Center of Solid Waste Management, Ministry Coordinating
Environmental ProtectionCentre for Asia and the Pacific
of China.
and National Center of Solid Waste Management, Ministry of Environmental Protection of China.

Keywords: brominated flame retardants (BFRs); waste electrical and electronic equipment (WEEE); printed circuit boards(PCBs);
GC/MS

1. Introduction

During the last decades, polybrominated diphenyl ethers (PBDEs)ǃpolybrominated biphenyls (PBBs)
and tetrabromobisphenol A (TBBPA)ǃhexabromocyclododecane (HBCD)ǃbrominated phenyl ethers
and bisphenol-A ethers have been among the group of commonly used as brominated flame retardants
(BFRs). Undoubtedly, these flame retardants benefit to mankind greatly since their application in
polymers[1-2]. Howereˈit was reported that PBDEs and PBBs are likely to bioaccumulate[3] , and have

* Corresponding author. Tel.: +86-10-62794351; fax: +86-10-62772048

E-mail address: jinhui@tsinghua.edu.cn.

1878-0296 © 2012 Selection and/or peer-review under responsibility of Basel Convention Coordinating Centre for Asia and the Pacific and National
Center of Solid Waste Management, Ministry of Environmental Protection of China
doi:10.1016/j.proenv.2012.10.076
 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559 553

been detected in various environmental samples[4-8], human tissue[9], and animal tissue[10] . Hence , to
protect and improve the quality of environment and human health, the directive 2002/95/EC (RoHS) by
the European Parliament prohibits the use of PBBs and PBDEs. The maximum permitted concentration of
these substances will be 0.1% by weight of homogeneous material(Directive 2002/95/EC)[11]. Therefore,
it’s essential to find a fast and reliable way to identify the BFRs in WEEE plastics.
Because of the diversity of BFRs, many analysis methods were used, such as gas chromatography with
mass spectrometric detection, GC/MS isotope dilution method[12] (Ikonomou and Rayne, 2002) and
HPLC/MS[13-14](Pettersson-Julander et al., 2004; Schlummer et al., 2005) have been published. But the
higher brominated PBBs and PBDEs(containing 8~10 bromine atoms), which were the most widely used
in electrical and electronic equipment, could not be analyzed by the first method. The latter two have
exigent requirements on instruments, skill of analysis and cost of operation, so it is quite difficult for
practical use. A GC/MS analytical method for the determination of PBBsǃPBDEs(with 1~10 bromine
substituents) and TBBPA was used to identify the BFRs in this study.

2. Material and methods

2.1. Chemicals and instruments

Standard solutions which all purchased from J&K Chemical Ltd were as follows:
dibromobiphenyl(D2BB), hexabromodiphenyl(H6BB), heptabromodiphenyl(H7BB),
octabromodiphenyl(O8BB), decabromodiphenyl(D10BB), tetrabromobiphenyl ether(T4BDE), P5BDE,
H6BDE, H7BDE, O8BDE, N9BDE, D10BDE, and TBBPA.
Solvents(chloroform, n-hexane, methanol) used for sample pretreatment were obtained from
Guangzhou Chemical Reagent Factory. All solvents were of analytical grade.
KQ-500DB Ultrasonic Bath(20 L bath volume, 40 KHZ ultrasonic frequency, 100 W power) from
Jiapeng Electronic Company, Wuhan, China

2.2. Gas chromatography (GC-6890,Agilent) and inert mass spectrometry (MS-5973, Agilent), with a KL-
PBB capillary column (15 m ×0.25 mm, film thickness 0.10 ȝm), Palo Alto, CA, USA. Subjects

Three kinds of WEEE plastics and a kind of printed circuit boards scraps were collected from a WEEE
dismantling plant in Guang Zhou of China. Detailed information is listed in Table 1.

Table 1 Samples investigated in this study

Sample name Polymer type Abbreviation Description

1 printed circuit boards PCB Roughly-cut scraps

2 polycarbonate PC Cell phone shells

3 acrylnitrile-butadiene-styrene ABS Computer housings

554 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559

4 high impact polystyrene HIPS TV housings

2.3. Sample treatment

The four samples(5±1 g) were embrittled with liquid nitrogen and ground to a particle size less than 20
mesh. Three portions from the ground sample of 1 g each were placed in three serum bottles, and then
added 30 ml solvent under the leaching conditions of a liquid-to-solid ratio of 30:1. After marinating for
24 h, the samples were subjected to ultrasonic extraction for 30 min thrice. then collected the extractant
by filteration with 1.2 ȝm glass fiber filters. Because the samples contain high polymer components, the
high polymer parts will dissolve in the solvent and cause an increase in the viscosity of extracts, which
will block the injector of GC. In that case, methanol was added into filtrate to deposit the high polymer
parts, and the limpid solution could be concentrated by K-D concentrator at the temperature about 70ć to
1 ml for analysis.

2.4. Analytical method

The analytical conditions of GC/MS were as follows: carrier gas, helium with a flow pressure of 100
kPa; column temperature program, oven temperature at 280ć for 0.5 min, and then increased to 330ćfor
1.5 min at the rate of 10 ć/min; injection volume, 1 ­L; split ratio,10:1.The MS operating parameters
were: ionization model, EI; electron energy, 70 eV; ion source temperature, 230 ć ; quadrupole
temperature, 150ć; translating line temperature, 280ć; the mass scan range from 200 to 800 u; Em
voltage, 2300 V.

3. Results and discussion

Fig. 1 shows the total ion chromatogram from GC/MS analysis of the standard mixture. The
parameters of every standard chemical are listed in Table 2.
 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559 555

Fig.1 The chromatograms of standard mixture obtained from GC/MS. The mixture contained 100ppm of PBDEs(4Br-10Br),
PBBs(2Br-10Br), and TBBPA respectively

Table 2. Specific ions of several PBDEs and PBBs

Peak No. Retention Analyte Characteristic masses Molecular mass

time(min)
1 0.605 D2BB 310,312,314 312
2 0.862 T4BDE 324,326,328; 484,486,488 486
3 1.059 P5BDE 404,406; 562,564,566,568 565
3ƍ 1.220 P5BDE
4 1.497 H6BB 306,308,310; 466,468,470;546,548; 625,627,629 628
5 1.579 TBBPA 259,293;449;503,529,568 502
6 1.702 H6BDE 482,484,486; 546,548,550,552;641,643,645 644
7 1.988 H7BDE 279,281,283,285; 559,561,563,565; 719,721,723,725 723
8 2.076 H7BB 545,547; 624,626,628; 703,705,707,709 707
9 2.714 O8BDE 639,641,643; 797,799 802
9ƍ 2.803 O8BDE
10 2.910 O8BB 463,465,467; 543,545; 703,705; 782,784,786 786
10ƍ 3.504 O8BB
11 3.745 N9BDE 360,362; 719,721 881
12 4.355 D10BB 312;391;463;544; 621,623,625; 781,783,785 944
13 5.535 D10BDE 399,401; 458,460;530,532;639,690;721,799 960

3.1. Total ion chromatogram of different samples and determined concentration

Typical chromatograms of different samples are shown in Fig. 2(a-d). And the detailed information
was listed in Table 3. Compare the parameters of every substance with those of standard solution.
Meanwhile, when use the mass spectral reference library(Wiley7n.L and WHQ.L), the objective
substances were obtained quickly. It is clear to find out that the PBBs were not detected in the four
samples, and one sample of WEEE plastic had more than one kind of BFRs. The important reasons
analyzed were as follows: (1) the price of PBBs are relatively higher, in view of product cost, many
producers did not select this kind of BFR; (2) some amount of flame retardants decomposed during the
period of the electrical and electronic equipment in use of being heated and sunlight irradition; (3) the
collected WEEE palstics were from different trademarks.
The ion chromatograms of the four samples in detail and their comparision with those of the standard
mixture have been shown in Fig. 2 and Table 3. The PCBs contained P5BDE and H6BDE, with the
contents of14567 mg/kg and 2718 mg/kg respectivelyˈthe amount exceeded the ROHS restriction.
Interestingly, none of any BFRs was detected in cell phone shells(Fig.2 (b)).
Based on the identification of BFRs from computer housings, there were five kinds of BFRs, 2,4,6-
tribromophenol(TBP), TBBPA, H7BDE, O8BDE, and N9BDEˈhaving the contents of 3449 mg/kgˈ
15804 mg/kgˈ1540 mg/kgˈ1340 mg/kgˈand 180 mg/kg respectively. Obviously, the content of
TBBPA was much more higher than the other four. The BFRs content in TV housings, H7BDE, O8BDE,
556 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559

and N9BDE were1471 mg/kgˈ467 mg/kg, and 5.3 mg/kg respectively, in which N9BDE was extremely
low, near by the detection limit(5 mg/kg).

Fig. 2. Ion chromatograms obtained from GC/MS analysis of different samples: (a) printed circuit boards scrap(sample 1), (b)
mobile phone shells(sample 2),(c) computer housings(sample 3), and (d) TV housings(sample 4

3.2. The reasons that different BFRs appear in one kind of WEEE plastics

It is well known that D10BDE is one of the widely used BFRs, however, many low BDEs(P5BDE,
H6BDE, H7BDE, O8BDE, N9BDE) but not the D10BDE were detected in the samples used in this
experiment. As for these results, we could take into consideration the possibility of preferential
degradation of highly brominated diphenyl ethers, as observed by Rahman et al. , Watanabe and
Tatsukawa[15] and Pijnenburg et al.[10]. Particularly, Watanabe and Tatsukawa reported that D10BDE
was vulnerable to photolytic debromination, resulting in the formation of less brominated PBDEs
congeners. Because the samples were collected from landfill and exposed to sunlight, the degradation
might have been taken place.
 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559 557

TBBPA is used both as an additive and a reactive flame retardant in the manufacture of polycarbonate
resins. Phenolic and epoxy resins are usually used for printed circuits boards which are responsible for the
spread of materials containing BFRs. But in this study, TBBPA was not detected from PCB. This result is
not unreasonable yet, it is reported[16] that FR-4 is fire retarded with TBBPA while FR-2 is fire retarded
with either TBBPA if the boards are manufactured in Europe or P5BDE if the boards are manufactured in
Asia, although the use of P5BDE is decreasing.

Table 3 Investigated parameters of the examined flame retardants

Sample Component Retention time (min) Relative area(%) Concentration(mg/kg)

1 P5BDE 1.206 37.52 14567
H6BDE 1.552 6.99 2718
2 None None None 0
3 TBP 0.985 21.83 3449
TBBPA 1.521 100 15804
H7BDE 2.009 20.12 1540
O8BDE 2.681 17.51 1340
N9BDE 3.685 2.36 180
4 H7BDE 2.010 24.26 1471
O8BDE 2.712 7.70 467
N9BDE 3.739 0.09 5.3

TBP was beyond expectant detected from the computer housings. It is generally believed that TBP
isn’t used as flame retardants in EEE or PCBs. As described by Marongiu, A., et al, TBBPA decomposes
in a temperature range between 200ć and 500ć, forming gaseous mixtures of HBr and harmful
compounds such as bromine-containing phenols, in which TBP is one of the important brominated
products[17] . As for the results in this study, the main reason was a little amount of TBBPA being
decomposed at the high injection temperature(330ć).

3.3. The relationship between different WEEE plastics and BFRs concentration

As the main flame retardant carriers, PCB should contain the most flame retardants. But in this study,
the total content was 17285 mg/kg, lower than those in computer housings 18864 mg/kg. The main
reasons are: (1) the total Br- content in waste PCB was about 6.78%, and 8.99% in virgin[18], (2) some
PCBs used in the study were incinerate into char, as for these two reasons, some flame retardants being
lost resulted in the decrease of flame retardants.
As for the results of PBDEs in computer housings and TV housings, it is noteworthy that congeners
from H7BDEs to O8BDEs were highly detected, while N9BDEs were very low, only 5.3 mg/kg in TV
housings. most likely, a large amount of high bromine BDEs decomposing contributed the main reason.
Brominated and chlorinated flame retardants are used in the epoxy resins of PCB and components in
mobile phones, especially, in charger. Moreover, it is counted that the weight of a phone charger is often
greater than the phone itself, and it is a major contributor to waste from cellular phones. In addition, the
PCB and liquid crystal display (LCD) of mobile phones account for about 98% (59% and 39%
respectively). However, in this study the experimental subject was mobile phone shells. No halogenated
flame retardants to have been detected was authentic.
558 Yuan Chen et al. / Procedia Environmental Sciences 16 (2012) 552 – 559

4. Conclusions

In this study, several RoHS relative BFRs have been detected with GC/MS; which are P5BDE,
H6BDE, H7BDE, O8BDE, N9BDE, and TBBPA from WEEE plastics and PCBs. Extraction solution
chloroform/hexane(1:1) can leach both polar(TBBPA) and unpolar(PBDEs) BFRs. During GC/MS
analysis, the separation time was only 6.5 min, it is much shorter than that used by Masahiro Osako (45-
50 min)[19] , Núria Fontanals(28 min)[20], and M.F. Fernandez (48.2 min).
From the results of BFRs in the selected four samples, the following conclusions may be drawn: (1) no
PBBs are detected; (2)moblie phone shells have no BFR, while H7BDE, O8BDE, and N9BDE are
frequently found in TV housings and computer housings. Except for these three congeners, TBBPA has
obviously been found in computer housings. As for PCBs, P5BDE and H6BDE are the main BFRs; (3)
the variety of BFRs in one sample is probably owing to the differences in trademarks, producers, and
degradation of highly brominated diphenyl ethers in landfill sites..

Acknowledgements

We gratefully acknowledge financial support from the National Public Benefit (Environment) Research
Foundation of China (No. 2010467026) and special fund of State Key Joint Laboratory of Environment
Simulation and Pollution Control (No. 11Z02ESPCT).

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