Policy Analysis

pubs.acs.org/est

RoHS regulated Substances in Mixed Plastics from Waste Electrical

and Electronic Equipment
Patrick A. Wag er,,* Mathias Schluep, Esther Muller, and Rolf Gloor

Technology and Society Laboratory, Swiss Federal Laboratories for Materials Science and Technology (Empa), Lerchenfeldstrasse 5,
9014 St. Gallen, Switzerland

Bachema AG, Rutistrasse 22, 8952 Schlieren, Switzerland

S Supporting Information
*

ABSTRACT: The disposal and recovery of plastics from waste

electrical and electronic equipment (WEEE) are of considerable
importance, both from an environmental and an economic perspective.
This paper presents the results of a study investigating current
concentrations of hazardous substances in mixed plastics from WEEE
and their implications for an environmentally sound recovery. The
study included 53 sampling campaigns for mixed plastics from WEEE.
The samples were analyzed with regard to heavy metals (cadmium,
chromium, mercury, and lead) and flame retardants (PentaBDE,
OctaBDE, DecaBDE, DecaBB) regulated in the RoHS Directive. Besides these substances, other brominated flame retardants
known to occur in electronics (HBCD, TBBPA) as well as the total bromine and phosphorus contents were considered. Results
show that no mixed plastics fraction from WEEE is completely free from substances regulated in the RoHS Directive. The lowest
number and average concentrations were found in flat screen monitors. The highest concentrations were found in mixed plastics
from CRT monitors and TVs. Mixed plastics fractions with high average concentrations of heavy metals originate from the
treatment of small household appliances (cadmium), ICT equipment (lead), and consumer equipment (lead). Mixed plastics
fractions with high average concentrations of brominated flame retardants mainly originate from the treatment of small
household appliances for high temperature applications (DecaBDE), CRT monitors (OctaBDE and DecaBDE) and consumer
equipment (DecaBDE), in particular CRT TVs (DecaBDE). To avoid a dissipation of hazardous substances into plastics and the
environment, it is recommended that mixed plastics from WEEE are subject to a strict quality management.

INTRODUCTION
In 2008, the plastics share from European waste electrical and
electronic equipment (WEEE) over all categories was estimated
to amount to 20.6%.1 For the members of the WEEE Forum,2
whose members collected and treated about 1.5 million tonnes
of WEEE in 2008,3 this corresponds to about 300 000 tonnes of
plastics waste recovered or disposed of in the same year.
The disposal and recovery of plastics from WEEE are of
considerable significance, both from an environmental and an
economic perspective. In particular, plastics from WEEE may
contain hazardous substances such as cadmium, lead, or
brominated flame retardants (see refs 412), which on the
one hand are associated with risks for health and the
environment and on the other hand may give rise to high
processing costs, depending on the disposal or recovery route
chosen.1315
For newly marketed EEE, maximum concentration values for
selected heavy metals and brominated flame retardants have
been defined in the Directive 2002/95/EC of the European
Parliament and of the Council on the restriction of the use of
certain hazardous substances in electrical and electronic
equipment (RoHS Directive).16 According to the Directive,
the Member States are expected to make sure that from July 1,
2006, newly marketed EEE shall not contain any lead, mercury,
2011 American Chemical Society

cadmium, hexavalent chromium, polybrominated biphenyls

(PBB) or polybrominated diphenyl ethers (PBDE) in
concentrations above-defined maximum concentration values
(MCVs) for homogeneous materials.17 This also includes
DecaBDE, which had been specifically exempted from the
RoHS Directive on October 15, 2005 by the European
Commission, based on the conclusions of risk assessments on
environmental and human health. In January 2006, however,
the European Parliament and Denmark launched legal
proceedings against this exemption, which led to the annulation
of the Commission Decision on grounds of procedural errors
by the European Court of Justice.18
As a consequence, the WEEE Forum commissioned the
Swiss Federal Laboratories for Materials Science and
Technology (Empa) to perform a study, which provides a
comprehensive empirical foundation regarding the levels of
substances regulated by the RoHS Directive in mixed plastics
from the treatment of the quantitatively most relevant
categories defined in the European WEEE Directive.19 In
Received:
Revised:
Accepted:
Published:
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July 21, 2011

October 10, 2011
November 29, 2011
November 29, 2011
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Policy Analysis

the plastics chips differed considerably from less than 2 mm

diameter to several cm of edge length.
In a second step the grain size of the plastic fraction was
reduced to <0.5 mm in consecutive steps (reduction to <6 mm,
then to <2 mm, and finally to <0.5 mm) by milling and sieving
with a high performance cutting mill and sieves with different
mesh sizes. While in the first reduction step (<6 mm) the
whole available plastic fraction was cut, for the consecutive
steps the sample size was each reduced to a homogeneous,
representative fraction with a riffle splitter according to the
procedure described in ref 24. The amount of sample entering
the last step corresponded to about 200250 g. Finally, about
80 g of the resulting fraction with a grain size of <0.5 mm were
ground to a particle size of <0.12 mm by an ultracentrifugal
mill, under application of liquid nitrogen.
In order to address the question as to whether the elevated
lead concentrations found in some samples might be the
consequence of a cross contamination from, for example, circuit
boards during the shredding process, additionally to the
standard sample conditioning process three samples were
washed with a Nanopure distilled water spray25 in the 2 mm
sieving step.
Chemical Analyses. Mixed plastics samples were analyzed
with regard to the following elements and compounds:
Heavy metals regulated by the RoHS directive: cadmium,
chromium, lead and mercury.
Brominated flame retardants regulated by the RoHS
Directive: PentaBDE, OctaBDE, DecaBDE.
Other brominated flame retardants: HBCD, TPPBA.
Other elements such as bromine and phosphorus.
Semiquantitative Analyses. A series of elements including, among others, bromine, cadmium, chromium, lead,
mercury, and phosphorus, were semiquantitatively analyzed
with X-ray Fluorescence (XRF) spectrometry. In a first step, a
quantity of the dried and ground laboratory sample was
introduced into a cuvette so that its bottom was fully covered
with the sample and the layer thickness corresponded to about
1 cm. The cuvette was then transferred into the automatic
sampler of a Spectro X-Lab device and the analyses were started
by selecting the Turbo-Quant method. For each sample a single
measurement was performed.
The basic calibration of the device was performed by the
equipment manufacturers (SPECTRO GmbH). The TurboQuant method had been calibrated with many different
matrices by the laboratory performing the analysis and was
suitable for analyses of samples not of geological origin.25
The detection limits for each of the elements analyzed
depended on the calibration performed. The extended,
combined uncertainty for the determination of bromine,
cadmium, chromium, lead, mercury, and phosphorus exceed
the uncertainties for samples of geological origin (1225%) by
a factor of 2, that is, they amount to about 2550%.25,26
Quantitative Metals Analyses. The quantitative analyses
of cadmium, chromium, lead, and mercury each included a
closed vessel microwave digestion followed by a specific
chemical analysis. For every plastics sample three digestions
and analyses were performed.
Digestion followed a two-step procedure including addition
of 5 mL of HNO3 65% and 3 mL H2O2 30% to 0.3 g of the
dried and ground sample in the first step, and of 3 mL of HCl
37% in the second step. In parallel, for some of the first samples
an additional one-step digestion of 0.5 g of the dried and

2008 these were large household appliances (category 1, 45.4%

of the total WEEE amount), small household appliances
(category 2; 10.6%), IT and telecommunications equipment
(category 3; 16.4%), and consumer equipment (category 4;
21.0%).1,20
In this paper we present the results of the study, which
intended to provide answers to the following two key
questions:
What are the current concentrations of substances
regulated by the RoHS Directive in mixed plastics from
selected WEEE categories and products?
What are the implications for an environmentally sound
recovery of plastics from WEEE?

MATERIALS AND METHODS

Mixed Plastics Sampling. The sampling strategy was
defined based on the results of an extensive literature review
and a comprehensive expert consultation.20 It addressed mixed
plastics stemming from the pretreatment of the following
WEEE flows:
Mixed WEEE categories as typically processed by
European WEEE recycling companies.
WEEE categories 1, 2, 3, and 4.
WEEE products expected to either contain particularly
high levels of RoHS substances (e.g., CRT monitors/
TVs, small appliances for high temperature applications)
or especially low levels (e.g., flat screens) in their
respective plastics fraction.
Under consideration of the existing standards DIN EN
1489921,22 and LAGA PN 98,23 a sampling procedure was
developed. According to this procedure, mixed plastics samples
from maximally 20 tonnes of input WEEE material were taken
under the responsibility of those 15 members of the WEEE
Forum that had previously agreed to participate in the sampling
campaign. An overview of the WEEE input material flows
considered in this study, as well as the number of mixed plastics
sampling campaigns performed and laboratory samples
analyzed is given in Table S1, Supporting Information (SI).
For every sampling campaign, eight single samples of defined
volumes were taken from the mixed plastics waste either from a
falling stream or, whenever that was not possible, from a
container. Two laboratory samples were provided by combining
and reducing four randomly selected single samples out of the
eight samples. Sample reduction was done by coning and
quartering. The volumes and amounts of the single and
laboratory samples corresponded to those defined in LAGA PN
9823 (see SI Table S2). With a view to an appropriate
evaluation of the results, every sampling campaign was
documented in a detailed sampling protocol.
As a general rule one randomly chosen sample from each
sampling campaign was subjected to further conditioning and
chemical analyses. In order to evaluate the uncertainties related
to sampling, repeated analyses were performed for nine
sampling campaigns selected to cover a wide range of different
samples. In addition, three samples were washed with distilled
water prior to their analysis to evaluate the effect of crosscontaminations (see SI Table 3).
Laboratory Sample Conditioning. In a first step all
metals except stranded copper wire and thin nonmagnetic
cables were removed by magnet and hand sorting from the
delivered sample (15 kg), and the resulting plastic and metal
fractions each weighed. Depending on the sample, the sizes of
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Figure 1. Concentration ranges of heavy metals in the mixed plastics fractions, allocated to each WEEE categories 1, 2, 3, and 4. (C1: Large
household appliances w/o cooling appliances {5}; C2: Small household appliances {2}; C3: ICT equipment w/o CRT- and flat screens {2}; C4:
Consumer equipment w/o CRT- and flat screens {1}; M1: Small appliances w/o CRT- and flat screens {7}; M2: Small household appliances, tools,
toys, leisure, and sport equipment {2}; M3: ICT and consumer equipment w/o CRT- and flat screens {2}; P11: Cooling and freezing appliances
(inside lining without drawers) {5}; P12: Cooling and freezing appliances (all plastics, except foams) {6}; P22: Vacuum cleaners w/o hoses {1};
P23: M2 w/o vacuum cleaners {1}; P24: Small appliances for high-temperature applications (e.g., toasters, hair dryers, curlers) {1}; P31: CRT
monitors {5}; P32: Flat screens {5}; P33: Printers {3}; P41: CRT TVs {7}; P42: Flat screen monitors {1}). {}: Number of sampling campaigns.

For each of the analyzed samples, three measurements per

element were performed. According to,26 the extended,
combined uncertainty for the determination of cadmium,
chromium, lead and mercury amounts to 1225%. For
chromium, the analysis with aqua regia in plastic material is
known to result in a systematic underestimation of this
element. This could be demonstrated with a certified reference
material (ERM EC 681 K). As a consequence, the chromium
content was finally determined by XRF spectrometry (see
above), which delivers more accurate results despite higher
uncertainties.25
Quantitative Analysis of Brominated Flame Retardants. Each 0.5 g of the sorted, reduced, and ground samples
were extracted with 100 mL of a mixture of cyclohexane and
acetone (1:1) in a Soxhlet extractor for 16 h at a minimum.
Subsequently, the extracted compounds were derivatized for 60
min at 70 C after having added 40 L of toluene and 20 L of
trimethylsilyl N,N-dimethylcarbamate (DMCTMS) or silyl-991
(a mixture of N,Obis(trimethylsilyl)trifluoroacetamide and
trimethylchlorosilane at a ratio of 99:1) to 40 L of the extract.
One to 2 L of the extract each were injected on a splitless
injector BGB-1 10 m 0.25 mm 0.1 m capillary column
with a GC PAL autosampler. After separation in a Trace GC

ground sample with 2 mL of HNO3 65% and 6 mL HCl 37%

(aqua regia) was performed. A comparison of the results from
the application of the two digestion methods showed no
significant difference.
Cadmium was determined by inductively coupled plasma mass spectrometry (ICP-MS) with an Agilent 7500ce, Octopole Reaction System. Calibration was performed with
cadmium isotope 111 at concentrations of 0, 1, 5, and 10
g/L.
Lead and chromium were determined by inductively coupled
plasmaoptical emission spectrometry (ICP-OES) with a
Varian 735-ES device. The lead concentrations were measured
at a wavelength of 200.353 nm, and the calibration was
performed at concentrations of 0, 0.2, 1.0, 2.0, and 10 mg/L.
The chromium concentrations were measured at a wavelength
of 205.56 nm, and the calibration was performed at
concentrations of 0, 0.1, 0.5, 1.0, and 5.0 mg/L.
Mercury was determined by atomic fluorescence spectrometry (AFS) at 253.7 nm with an Analytik Jena Mercur device
after reduction with an SnCl2-solution and scavenging into a
fluorescence cuvette. Calibration was performed at concentrations of o 0, 10, 50, and 100 ng/L.
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Figure 2. Concentration ranges of specific BFRs in the mixed plastics fractions, allocated to each WEEE categories 1, 2, 3, and 4 (C1: Large
household appliances w/o cooling appliances {5}; C2: Small household appliances {2}; C3: ICT equipment w/o CRT- and flat screens {2}; C4:
Consumer equipment w/o CRT- and flat screens {1}; M1: Small appliances w/o CRT- and flat screens {7}; M2: Small household appliances, tools,
toys, leisure, and sport equipment {2}; M3: ICT and consumer equipment w/o CRT- and flat screens {2}; P11: Cooling and freezing appliances
(inside lining without drawers) {5}; P12: Cooling and freezing appliances (all plastics, except foams) {6}; P22: Vacuum cleaners w/o hoses {1};
P23: M2 w/o vacuum cleaners {1}; P24: Small appliances for high-temperature applications (e.g., toasters, hair dryers, curlers) {1}; P31: CRT
monitors {5}; P32: Flat screens {3}; P33: Printers {3}; P41: CRT TVs {7}; P42: Flat screen monitors {1}). {}: Number of sampling campaigns.

Ultra (make up gas N2 5.0 30 mL/min, carrier gas H2), the

brominated flame retardants were detected with an ECD Ni63
and quantified using a software. Calibration was done with the
pure compounds, namely BDE-47 (2,2,4,4-Tetrabromdiphenylether), BDE 99 (2,2,4,4,5-Pentabromdiphenylether), BDE183 (2,2,3,4,4,5,6-Heptabromdiphenylether), BDE-197
(2,2,3,3,4,4,6,6-Octabromdiphenylether), BDE-209 (DecaBDE), DecaBB (Decabrombiphenyl), HBCD (Hexabromocyclododecane), and TBBPA (Tetrabromobisphenol-A). The
concentration range for the calibration lay between 0.01 and
0.5 g/mL, and the extraction was controlled for losses with
4,4-Dibromooctafluorobiphenyl (DBOFB).
The concentrations of the technical mixtures of Penta- and
OctaBDE (CDE71 and CDE79) required for the evaluation of the
samples with regard to the RoHS Directive were calculated on
the basis of the measured concentrations of BDE-47, BDE-99,
BDE-183, and BDE-197 (CBDE47, CBDE99, CBDE183, and
CBDE197) according to the following equations:

The factors had been obtained from the analysis of different

commercially available technical mixtures and extensive round
robin tests (unpublished data). Detection limits were
0.02 g/kg for BDE-47, BDE-99, BDE-183, BDE-197,
DecaBB, and TBBPA;
0.05 g/kg for DE-71 (Great Lakes, Pentas) and DE-79
(Great Lakes, Octas);
0.1 g/kg for BDE-209;
0.2 g/kg for HBCD.
The applied procedure basically corresponds to the
specifications in DIN EN 62321,27 which is typically used to
evaluate electrotechnical products with regard to substances
regulated in the RoHS Directive. It differs from DIN EN 62321
in that
the samples were not extracted with toluene, because the
recovery for TBBPA appeared to be too low; instead, a
mixture of cyclohexane and acetone was used (see
above);
the measurements were performed with an ECD and not
with an MS-detector;
the extracts were derivatized in order to be able to
determine TBBPA.

CDE71 = (CBDE47 + CBDE99) 1.3

CDE79 = (CBDE183 + CBDE197) 1.4

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Cadmium was detected in concentrations which lie close to

or above the respective RoHS MCV of 100 ppm in mixed
plastics from small household appliances categories (C2, M2,
P23). In all other mixed plastics samples the concentrations
were found to lie between 2 and 62 ppm (averages: 230
ppm), with the highest concentrations in mixed plastics from
TV monitors. A 10 year old study demonstrated similar
concentrations in plastics from CRT monitors and TVs, albeit
with 25% of the samples clearly exceeding the RoHS MCV.7
Similarly Schlummer et al.4 found elevated cadmium concentrations in the range of the corresponding RoHS MCVs in
WEEE shredder residues from television (TV) set housings,
monitor housings and mixed sources, and elevated lead
concentrations in mixed WEEE shredder residues. Our results
suggest that mixed plastics from household appliances are the
main source for cadmium, with concentrations dropping to the
level of the RoHS MCV and below within the past decade.
For some mixed plastics from WEEE category 1 to 3 devices
(M2, P23), unspecified chromium was detected at concentrations near to or above the RoHS MCV defined for
hexavalent chromium in all samples; in mixed plastics from
WEEE category 4 devices, concentrations were lower than the
MCV by at least a factor of about 2. Except for category 4
devices, our results do not allow one to exclude the possibility
that the hexavalent chromium concentrations might exceed the
respective RoHS MCV.
Mercury was detected in all samples at levels of at least 2
orders of magnitude below the corresponding RoHS MCV.
This is in accordance with the findings of other studies, where
mercury was not found in relevant concentrations in mixed
plastics from WEEE (see. e.g.4).
Brominated Flame Retardant Concentrations. Figure 2
displays the concentration ranges for the brominated flame
retardants TBBPA, PentaBDE, OctaBDE, and DecaBDE in
WEEE for each of the four WEEE categories. For a full list of all
laboratory analyses results see SI Table S4. DecaBB and HBCD
were not considered, because they were either only found at
concentrations not exceeding 0.5 g/kg (DecaBB in CRT TVs)
or not found above the detection limit at all (HBCD). For the
calculation of average values, concentrations measured below
detection limits were approximated with the detection limit,
which corresponds to a worst case perspective. For the
evaluation of the single PBDE we referred to the RoHS
MCV for PBDE, although it applies for their sum. However, as
can be derived from the detailed laboratory analyses results in
the SI Table S4, the sum of the measured PBDE only exceeded
the MCV when the average concentration of one of the single
PBDE exceeded the MCV.
TBBPA was detected in most samples with average
concentration levels typically ranging from 1 to 10 g/kg. The
highest concentrations were found in mixed plastics from CRT
monitors (P31) with an average concentration of 37 g/kg and a
maximum level of 63 g/kg. The lowest detected value was
found in a single sample of mixed plastics from small appliances
for high-temperature applications (P24), namely 0.1 g/kg DM.
Mixed plastics from large household appliances (C1, P11, P12)
is the only category where TBBPA was not detected. Summing
up, the results suggest that TBBPA has to be expected in
concentrations between 1 and 10 g/kg or above in mixed
plastics from WEEE categories 24, whereas there are
indications that they do not occur in mixed plastics from
WEEE category 1. TBBPA concentrations found in category

According to ref 25, these changes do not distort the results

in terms of accuracy and recovery. The extended, combined
uncertainty for the determination of brominated flame
retardants with this method lies between 25% and 40%26. For
samples with elevated brominated flame retardant (BFR)
concentrations, repeated measurements were performed.

RESULTS AND DISCUSSION

Heavy Metals Concentrations. Figure 1 displays the

concentration ranges for heavy metals in the analyzed mixed
plastics (see SI Table 2), each allocated to WEEE categories 1
4. A full listing of all laboratory analyses results can be found in
SI Table S3. For the calculation of average values,
concentrations measured below detection limits were approximated with the detection limit, which corresponds to a worst
case perspective.
Lead concentrations in mixed plastics from WEEE were
found to range from 12 ppm (P41) up to 7800 ppm (M1). In
most samples, average lead levels were found to lie around the
RoHS MCVs of 1000 ppm. The MCVs are exceeded for all
mixed categories (M1M3) as well as for mixed plastics from
ICT equipment w/o CRT- and flat screen monitors (C3) and
mixed plastics from consumer equipment w/o CRT- and flat
screen TVs (C4). Concentrations above the MCV were also
found in one mixed plastics sample from printers (P33). In
mixed plastics from WEEE categories 1 and 2 (C1 and C2),
lead was found to lie in the vicinity of the RoHS MCV. Mixed
plastics from single product types also showed concentrations
close to the RoHS MCV with the exception of mixed plastics
from CRT monitors, flat screen monitors, CRT TVs and flat
screen TVs which contained less than 100 ppm of lead. While
this is in discordance with ref 5 where lead levels close to or just
above the RoHS MCV were found in plastics from CRT
monitors and TVs (as well as in other consumer equipment), it
confirms the results of ref 4
Elevated lead levels in mixed plastics could be the
consequence of cross contaminations from fractions such as
printed wiring boards, which had not been sorted out prior to
shredding.4 This hypothesis is supported by the fact that mixed
plastics samples with manual removal of the nonplastic
fractions before the shredding process (see P31 and P32 in
Figure 2, with concentrations around 100 ppm) showed
considerably lower levels of lead than mixed plastics samples
without prior removal of nonplastic fractions (see C3, C4, M1,
and M3 in Figure 2, with average concentrations between 131
and 7800 ppm). Further evidence comes from a simple test, in
which three mixed samples were analyzed after thorough
washing with a spray of distilled water (M1, M2 (M1, M2, and
P11). The results show that the lead concentration dropped
significantly in one sample (from 5300 to 160 ppm in an M2
sample), and slightly in two other cases (from 1800 to 1400
ppm in an M1 sample and from 1720 to 1340 ppm in a P11
sample). Although this is not a clear pattern, these results
suggest that lead levels which significantly exceed the RoHS
MCV indeed might have originated from cross contaminations
of lead containing components (e.g., circuit boards) in shredder
residues, and hence cannot be allocated to the plastic fraction
only. Still, our results do not exclude the possibility that the
elevated lead concentrations may be due to the presence of lead
containing plastics. In particular, polyvinyl chloride (PVC) for
cables and wires is known to contain lead compounds added as
a stabilizer.28
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all mixed plastics addressed in this study (see SI Figure S1).

This suggests that these appliances also contain other BFRs not
specifically addressed in this study; important representatives of
novel BFRs are, for example, decabromodiphenyl ethane or
1,2-bis(pentabromodiphenyl)ethane (DBDPE), 1,2-bis(2,4,6tribromophenoxy), ethane (BTBPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB or EHTBB), bis(2-ethylhexyl)-3,4,5,6tetrabromo-phthalate (TBPH or BEHTBP), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE), and
hexachlorocyclopentadienyldibromo-cyclooctane
(HCDBCO).12,32,33 A recent Swiss study, which investigated
1359 new products, found that in 476 components, mostly
originating from automatic dispensers, consumer electronic
devices and lighting equipment, the bromine contents exceeded
500 g/kg. The analysis of a subset of 214 samples with regard
to their contents of target compounds TBBPA, HBCD,
PentaBDE (technical mixture BDE 71), OctaBDE (technical
mixture BDE 79), DecaBDE and PBB showed that 60 samples
contained these target compounds and 72% some other,
unspecified brominated compounds.12,34
This is also true for plastics in vacuum cleaners (P23) and
small appliances for high-temperature applications (P24),
where the expectation that they might contain particularly
high levels of BFRs regulated by the RoHS Directive could not
be confirmed. Differences between directly measured and
calculated bromine contents were found to be largest for mixed
plastics from WEEE categories 3 and 4.
Total Phosphorus Content. Phosphorus flame retardants
(PFRs) such as bisphenol A bis(diphenyl phosphate) (BDP)
and resorcinol bis(diphenyl phosphate) (RDP) are typically
used in ABS/polycarbonate (PC) blends. Phosphate esters
being susceptible to hydrolysis, recycling of ABS/PC containing
these flame retardants may face some difficulties under
conditions of heat and humidity.35 Typically, PFRs are applied
at much lower concentrations than BFRs and hence are more
difficult to analyze.36
The results of the analyses of phosphorus in WEEE plastics
(see SI Figure S2) show that total phosphorus concentrations
in the analyzed plastic samples lie in the range between 1 g/kg
and 35 g/kg. This range corresponds to the reported amounts
of PFRs typically applied in EEE plastics35). The highest
phosphorus concentrations were found in mixed plastics from
flat screens TVs (P32, average 23 g/kg, maximum 35 g/kg),
CRT monitors (P32, average 7 g/kg, maximum 14 g/kg), CRT
TVs (P41, average 5 g/kg, maximum 9 g/kg) and consumer
equipment w/o CRT and flat screens (C4, 5 g/kg). These
findings are in line with the recent trend that PFR containing
ABS/PC is substituted for ABS containing BFRs. In the case of
consumer products, poly(p-phenylene oxide) (PPO) is
substituted for ABS containing BFRs.37 Below concentrations
of 5 g/kg, phosphorus was detected in mixed plastics from large
household appliances (C1) as well as from mixed WEEE
categories M1 and M3. All other samples did not contain
phosphorus above the detection limit of 0.1 g/kg.
Uncertainties. Uncertainties in the results presented above
are a combination of deviations related to sampling and the
combined uncertainties in the chemical analysis. While
uncertainties from the chemical analysis are quantitatively
described in the Materials and Methods section, repeated
analyses were performed for nine samples in order to allow for
a qualitative evaluation of uncertainties related to sampling. The
results of the repeated analyses are presented in SI Figures S2
and S3.

24 samples are most probably a consequence of its application

in acrylonitrile butadiene styrene (ABS) plastics.8
PentaBDE only could be found in a mixed plastics sample
from mixed small appliances w/o CRT- and flat screens (M1)
and from consumer equipment w/o CRT- and flat screens
(C4) at maximum concentrations of 0.14 and 0.13 g/kg,
respectively. This suggests that PentaBDE no longer occurs in
mixed plastics from WEEE in relevant concentrations, a finding
supported by previous studies, (see, for example, refs 4,911).
OctaBDE was detected at concentrations above the RoHS
MCV of 1 g/kg in mixed plastics from ICT and consumer
equipment w/o CRT- and flat screens (M3, average 1 g/kg,
maximum 1.6 g/kg), from CRT monitors (P31, average 2.5 g/
kg, maximum 10.6 g/kg) and from CRT TVs (P41, average 0.9
g/kg, maximum 3.5 g/kg). In mixed plastics from small
appliances w/o CRT- and flat screens (M1), from ICT
equipment w/o CRT and from flat screens (C3), OctaBDE was
found in concentrations close to the RoHS MCV. In mixed
plastics from consumer equipment w/o CRT- and flat screens
(C4), OctaBDE was detected at levels well below the RoHS
MCV (0.15 g/kg). OctaBDE was not detected in mixed plastics
from large household appliances. These results correspond to
those obtained in previous studies,4,9,10 where levels clearly
above the RoHS MCV were detected in mixed plastics from
CRT monitors and TV sets, and concentrations in the vicinity
of the RoHS MCV in mixed plastic fractions from mixed WEEE
categories. The measured average concentrations confirm
typical ranges of OctaBDE concentrations in plastics from
WEEE as indicated by ref 11; however, these ranges might be
clearly exceeded in individual mixed plastics samples from CRT
monitors.
OctaBDE has been mainly used for ABS plastics in the past,29
which has a particularly high share in ICT equipment (see ref
20). Hence, ABS is expected to be the main source for the
elevated OctaBDE concentrations measured in mixed plastics
from ICT equipment (and CRT monitors, in particular).
DecaBDE was measured at concentrations close to or above
the RoHS MCV in almost all samples. The highest
concentrations were found in mixed plastics from CRT
monitors (P31, average 3.2 g/kg, maximum 7.8 g/kg) and
from CRT TVs (P41, average 4.4 g/kg, maximum 7.8 g/kg). In
mixed plastics from mixed small household appliances (C2) as
well as from flat screen monitors and TVs (P32 and P42),
DecaBDE concentrations did not exceed the detection limit.
These results correspond to those obtained in previous studies
(see refs 4,9,10) and confirm the range of DecaBDE
concentrations in plastics from WEEE as indicated by;11 still,
these ranges might be clearly exceeded in individual mixed
plastics samples from CRT monitors and TVs.
DecaBDE is typically used in high impact polystyrene
(HIPS) plastics and ABS (e.g., for monitors and TV sets) or in
polypropylene (PP) (e.g., for large household appliances and
small appliances for high-temperature applications).30,31 Considering the shares of plastic types in different WEEE product
types (see ref 20), ABS appears to be the main source for
DecaBDE in mixed plastics from WEEE categories 2 and 3, as
well as in cooling and freezing appliances, and HIPS the main
source of DecaBDE in CRT TVs and other consumer
equipment.
The average bromine contents from total bromine measurements exceed the average bromine contents calculated from
measured concentrations for the specific BFRs (HBCD,
TBBPA, PentaBDE, OctaBDE, DecaBDE, DecaBB) in almost
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Environmental Science & Technology

Policy Analysis

DecaBDE and applies the limit value of 1 g/kg for PentaBDE

and OctaBDE each.
Our study indicates that WEEE plastics contain brominated
flame retardants which are not regulated by the RoHS Directive
and hence were not specifically measured in this study. As a
consequence it is suggested that further studies should be
dedicated to the identification of those substances and the
outcome of their risk assessment according to the REACH
Directive should be considered. In addition, our study indicates
that phosphorus based flame retardants are applied, in
particular, in WEEE category 3 and 4 appliances. Hence,
investigations destined to assess the impacts of a shift to
phosphorus based flame retardants with regard to inter alia
recyclability and environmental impacts should be considered
as well.

Differences in the heavy metal concentrations in separate

samples from the same sampling campaign are on the range of
the uncertainties related to chemical analysis for most samples.
This is an indication that deviations related to sampling do not
contribute to the overall uncertainty of the results. However,
exceptions from this finding can be seen for mercury in the C2
sample. It is assumed that this deviation is due to
inhomogeneity concerning the occurrence of mercury in the
sample.
The comparison of brominated flame retardant concentrations in separate samples from the same sampling campaign
presents a less clear picture. Differences close to 1 order of
magnitude can be observed for TBBPA (C2), OctaDBE (M2,
M3), and DecaBDE (P24). For TBBPA, the differences appear
on a range clearly below RoHS MCV for other compounds;
hence, they do not have any effect on the outcome of this
study. For OctaBDE and DecaBDE, however, they occurred on
the range of the RoHS MCV for the M3 and the P24 sample,
respectively. This stands in contrast to a correctly performed
sampling campaign in the case of these two samples, which
does not give any indication of a lack of homogeneity between
the repeated samples. Moreover, the repeated analysis for heavy
metals, where deviations are small for the same M3 and P24
sample, indicate homogeneity between the repeated samples.
Possible explanations for the deviations can only point in the
direction of large differences between the OctaBDE and
DecaBDE concentrations in the specific appliances within the
mixed samples, whereas sample preparation for the chemical
analysis would have picked shredder pieces with rather low
concentrations in one case and with rather high concentrations
in the other case. This would be possible if the shredder pieces
analyzed were too large compared to the size of the shredded
appliances, which might e.g. be the case in the respective M3
and P24 samples, both containing rather small appliances and
shredder pieces of up to several cm of edge length.
Although the above discussion leaves some questions open,
we do not expect that uncertainties in sampling and chemical
analysis would hamper the validity of our results. Both the
sampling procedure and chemical analysis followed common
standards as described in the Materials and Methods section.
Moreover, BFR concentration ranges found in this study
correlated with findings in previous studies as presented in the
introduction of this paper.
Implications for Recyclers and Further Research. The
results of the sampling campaigns show that no mixed plastics
fraction from WEEE is completely free from substances
regulated in the RoHS Directive. All the investigated mixed
plastics fractions contained at least one substance regulated by
the RoHS Directive in measurable amounts. To avoid a
dissipation of hazardous substances into plastics and the
environment, it is recommended that mixed plastics from
WEEE are subject to a strict quality management. Plastics
should be traced throughout the entire recycling chain, from
the moment they are generated up to the point where they are
either reintegrated into new products or properly disposed of.
Recyclers should ensure that they either can separate RoHS
regulated substances or the plastics containing these substances
and dispose them of properly. The plastics fraction destined for
reuse in new products should comply with the RoHS Directive,
unless there is clear evidence that it is not reintegrated into new
EEE products. In that case, the REACH Directive38 applies,
which is less strict with regard to PBDEs, as it does not include

ASSOCIATED CONTENT

S Supporting Information
*

An overview of sampling campaigns (Table S1) and the

minimum volumes and amounts of single and laboratory
samples (Table S2); illustrations of the total bromine and
phosphorus contents (Figures S1 and S2) and the upper and
lower concentration levels for repeated samples (Figures S3
and S4); detailed tables of the chemical analyses results for
heavy metals (Table S3) and BFRs (Table S4). This material is
available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*phone: +41 58 765 78 45; e-mail: patrick.waeger@empa.ch.

ACKNOWLEDGMENTS
We are grateful to the European Community and the WEEE
Forum for having supported this project. A special thank goes
to all those members of the WEEE Forum who provided
laboratory samples. Furthermore, we would like to express our
gratitude to the Swiss WEEE system operators SENS and
SWICO, who initiated this project by supporting an extended
literature review. Finally, we would like to thank Andreas Buser
and Leo Morf for their substantial inputs to the literature
review, Thomas Ruddy for his English editing, and the three
anonymous reviewers for their most valuable comments.

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