Supplementary Material
Characterization of polychlorinated naphthalenes in stack gas
emissions from waste incinerators
Environmental Science and Pollution Research
Jicheng Hu, Minghui Zheng, Wenbin Liu, Changliang Li, Zhiqiang Nie, Guorui Liu,
Bing Zhang, Ke Xiao
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research
Center for Eco-Environmental Sciences, Chinese Academy of Sciences, P.O. Box
2871, Beijing 100085, China

Corresponding author. Tel.: +86 10 62849172; Fax: +86 10 62923563;
E-mail address: zhengmh@rcees.ac.cn (M. Zheng).
Lists of contents:

Sample preparation and analysis for PCDD/Fs, PCBs, HxCBz and PeCBz

Table S.1 Relative potency factors (RPFs) of the PCN congeners summarized by
by Noma et al. (2004)

Table S.2 Recoveries of sampling and internal standards in the samples.

Table S.3 Concentrations of PCDD/Fs, PCBs, PCNs, HxCBz and PeCBz in the
stack gas samples

Fig. S.1 Correlation among the concentrations of ΣPCN and other U-POPs

Fig. S.2 Ratios of some characteristic PCN congeners in technical formulations of
PCNs and PCBs
1
Sample preparation and analysis for PCDD/Fs, PCBs, HxCBz and
PeCBz
The sample extraction and cleanup procedure for PCDD/Fs, PCBs, HxCBz and
PeCBz were performed simultaneously with PCNs. The stack gas samples were
spiked with these labeled standards (13C12-PCDD/Fs,
13
C6-PeCBz besides
13
13
C12-PCBs,
13
C6-HxCBz and
C10-PCNs) before extraction. Then the sample extracts were
concentrated and subjected to a series of cleanups by adsorption chromatography,
including acid silica gel column, multilayer silica gel column and basic alumina
column. For acid silica gel column and multilayer silica gel column, 70 ml n-hexane
was used to the pre-clean the column before loading up the concentrated extract and
then eluted with 90 ml n-hexane. For the basic alumina column, samples were eluted
with 100 mL dichloromethane/hexane (5:95, v/v; for PCNs, PCBs, HxCBz and
PeCBz fractions) and then eluted with 50 mL dichloromethane/hexane (50:50, v/v; for
PCDD/Fs fraction). Finally, the extracts were concentrated to about 20 μL by rotary
evaporation and a gentle stream of nitrogen gas. Prior to injection, syringe standards
were added to the extracts.
Analysis of PCDD/Fs and PCBs were performed on Agilent 6890 gas
chromatography coupled with an Autospec Ultima high resolution mass spectrometer
with an electron impact (EI) ion source. The HRMS was operated in SIM mode at
over 10 000 of resolution. 1 μL of sample solution was injected in splitless mode.
DB-5 fused silica capillary column (60 m × 0.25 mm i.d. × 0.25 μm) was used for the
separation of congeners. Helium was used as the carrier gas with a constant flow of
2
1.2 mL/min. The electron emission energy was set to 35 eV and 38 eV for PCBs and
PCDD/Fs, respectively. The source temperature was 270 °C for PCDD/F and PCB
analysis. The oven temperature programs were employed as follows: for PCDD/Fs,
160 °C initial for 2 min; increased at 7.5 °C/min to an isothermal hold at 220 °C for
16 min; increased at 5 °C/min to an isothermal hold at 235 °C for 7 min; increased at
5 °C/min to an isothermal hold at 330 °C for 1 min. For PCBs, the initial oven
temperature was 120 °C; this was held for 1 min, and increased to 150 °C at a rate of
30 °C/min, ten from 150 to 300 °C at 2.5 °C/min and held for 1 min.
With regard to the analysis of chlorobenzenes, an Agilent 6890 gas
chromatograph equipped with a DB-5MS capillary column (30 m × 0.25 mm i.d. ×
0.25 μm) and interfaced to an Agilent 5973N MS was used. 1 μL of sample solution
was injected in splitless mode. The flow rate was set at 2.0 mL/min with helium as
carrier gas. The oven temperature programs were employed as follows: start 50 °C
held for 5 min, 50-80 °C at 3 °C/min, 80-180 °C at 5 °C/min held for 3 min.
180-280 °C at 20 °C/min held for 5 min. EI ion source was used, and the source
temperature was 230 °C. The electron emission energy was 70 eV. The data were
acquired in SIM mode. Two masses (m/z: 250.0 and 252.0) were used to monitor
PeCBz, m/z 258.0 and 260.0 were monitored for
13
C6- PeCBz. Two masses (m/z:
284.0 and 286.0) were used to monitor HxCBz, m/z 294.0 and 296.0 were monitored
for 13C6- HxCBz.
The detection limits and quantification limits were defined as 3 and 10 times the
signal-to-noise ratio, respectively. Blank experiments were carried out in each batch
3
of samples. Some high-chlorinated PCDD/F congeners were detected in the blank
sample, but their concentrations were all lower than 5% of that in the stack gas
samples. The PCDD/F concentrations in samples were not corrected with blank values
in this study. The recoveries of PCDD/F and PCB internal standards were in the range
of 54–116% and 62–125%, respectively, and met the analytical method requirement.
The recoveries of PeCBz and HxCBz internal standards were in the range of 40–70%
and 52–97%, respectively.
4
Table S.1 Relative potency factors (RPFs) of the dl-PCN congeners summarized by
Noma et al. (2004)
PCN congener
RPFs
PCN congener
RPFs
CN2
1.8×10-5
CN57
1.6×10-6
CN1
1.7×10-5
CN56
4.6×10-5
CN4
2.0×10-8
CN66/67
2.5×10-3
CN5/7
1.8×10-8
CN64/68
1.0×10-3
CN10
2.7×10-5
CN69
2.0×10-3
CN48/35
2.1×10-5
CN71/72
3.5×10-6
CN38/40
8.0×10-6
CN63
2.0×10-3
CN50
6.8×10-5
CN70
1.1×10-3
CN54
1.7×10-4
CN73
3.0×10-3
Table S.2 Recoveries of sampling and internal standards in the samples
Standards used
during recovery determination
Recoveries (%)
13
13
85-90
13
13
82-88
13
13
74-81
Labeled standards
sampling standards
C12-1,2,3,7,8-PeCDF
C12-1,2,3,7,8,9-HxCDF
C12-1,2,3,4,7,8,9-HpCDF
C12-1,2,3,4-TCDD
C12-1,2,3,7,8,9-HxCDD
C12-1,2,3,7,8,9-HxCDD
internal standards
13
62-88
13
68-86
C12-1234-TeCN
C12-1357-TeCN
13
C12-12357-PeCN
13
C12-123457-HxCN
74-81
13
63-84
13
56-87
13
42-81
C12-123567-HxCN
C12-1234567-HpCN
C12-12345678-OCN
5
Table S.3 Concentrations of PCDD/Fs, PCBs, PCNs, HxCBz and PeCBz in the stack gas samples
Plant
PCDD/Fs
PCBs
denotation
∑PCDDa
∑PCDFa
∑WHO-TEQ
∑PCBb
∑WHO-TEQ
∑PCNa
dl-PCN TEQs
PeCBz
HxCBz
(ng Nm-3)
(ng Nm-3)
(pg Nm-3)
(ng Nm-3)
(pg Nm-3)
(ng Nm-3)
(pg Nm-3)
(ng Nm-3)
(ng Nm-3)
MW1
9.13
4.18
258
157
7.12
29.3
198
954
123
MW2
8.83
2.51
95.3
192
6.12
16.8
6.43
56.3
49.3
MW3
61.7
17.7
945
75.9
39.7
238
18.6
2045
435
MW4
90.0
104
4009
224
764
302
32.9
5503
2677
MW5
2.10
0.881
201
21.6
10.2
68.6
3.09
288
1684
MW6
1.04
0.700
24.1
19.1
6.78
80.7
2.16
1196
5879
MW7
20.4
9.20
558
17.7
8.39
42.3
1.74
100
669
MW8
1.01
0.374
22.8
13.5
2.95
60.5
1.76
809
756
MW9
2.10
0.523
27.5
22.6
4.71
23.7
5.71
305
604
Mean
21.8
15.5
682
82.6
94.5
95.8
30.0
1251
1431
a
Sum of tetra- to octa-chlorinated homologue.
b
Sum of tetra- to deca-chlorinated homologue.
PCNs
6
CBz
R2 = 0.73
R2=0.46
R2 = 0. 74
R2 = 0.87
R2 = 0.87
R2 = 0.65
Fig. S.1 Correlation among the concentrations of ΣPCN and other U-POPs
7
10000
43
1000
4
Ratios
100
45
42
10
93
79
9
1
99
96
26
1
61
0.1
-1
CN1 to CN2
CN45/36 to CN42
CN66/67 to CN71/72
CN54 to CN53/55
CN5/7 to CN6/12
CN73 to CN74
Fig. S.2 Ratios of some characteristic PCN congeners in technical formulations of
PCNs and PCBs (Falandysz et al. 2000; Yamashita et al. 2000; Noma et al. 2004;
Falandysz et al. 2006a; Falandysz et al. 2006b)
References
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Environ Eng 41:291-301
Falandysz J, Nose K, Ishikawa Y, Lukaszewicz E, Yamashita N, Noma Y (2006b) HRGC/HRMS
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