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J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 4 ) XX XXXX
ScienceDirect
www.journals.elsevier.com/journal-of-environmental-sciences
3Q2
Peng Zhou, Jie Guo, Xiaoyu Zhou, Wei Zhang, Lili Liu, Yangcheng Liu, Kuangfei Lin
School of Resources and Environmental Engineering, East China University of Science and Technology,
Shanghai 200237, China. E-mail: zpsarka@126.com
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AR TIC LE I NFO
ABSTR ACT
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Article history:
A typical Printed Circuit Board (PCB) manufacturer, including six workshops, was chosen as
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the object of this study. During PCB processing, fine particulate matter and heavy metals
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(Cu, Zn, Pb, Cr, Cd and Ni) will be released into the air and dust, which then impact workers'
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health and the environment. The concentrations of total suspended particle (TSP), PM10 and
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PM2.5 in the off-site were 106.3, 90.0 and 50.2 g/m3, respectively, while the concentrations
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of TSP, PM10 and PM2.5 in the workshops ranged from 36.1 to 365.3, from 27.1 to 289.8 and
from 22.1 to 212.3 g/m3, respectively. Almost all six of the heavy metals were detected in
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Heavy metal
all of the particle samples collected from these workshops except Cd. For each workshop, it
PM2.5
was obvious that Zn was the most enriched metal in TSP, followed by Cu > Pb
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Dust
(Cr) > Ni > Cd, and the same trend was found for PM10 and PM2.5. In the dust samples, Cu
Risk assessment
(which ranged from 4.02 to 56.31 mg/g) was the most enriched metal, followed by Zn, Cr, Pb,
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PCB manufacturing
Ni and Cd, and the corresponding concentrations ranged from 0.77 to 4.47, 0.37 to 1.59, 0.26
Keywords:
to 0.84, 0.13 to 0.44 and nd to 0.078 mg/g, respectively. The health risk assessment showed
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that noncancerous effects are unlikely for Zn, Pb, Cr, Cu, Cd and Ni. The carcinogenic risks
for Cd and Ni were all lower than 106, except for Cr. This result indicates that carcinogenic
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risks for workers are relatively possible in the workshops. These findings suggest that this
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2014 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
Introduction
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http://dx.doi.org/10.1016/j.jes.2014.08.003
1001-0742/ 2014 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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1. Experimental
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The samples were collected on separated days between December 2011 and February 2012 with an interval of one month. All
samples were taken during working hours and under normal
operating conditions of the PCB plant. The PM samples were
collected simultaneously using median-volume samplers
(Laoying, Qingdao, China) at a flow rate of 100 L/min, and
the total volume of each sample was automatically computed
by a flow recorder. Particles were collected on pre-baked glass
fiber filters (GFFs) with a diameter of 11 cm. The sampler was
placed near the automatic line about 2 m away and 1.7 m above
the ground and sampling periods. During the sampling period,
the ranges of average ambient temperature and relative
humidity were 912C and 68%80%, respectively. After sampling, the loaded GFFs were weighed at constant temperature
and humidity, cut into strips using stainless scissors and stored
at 20C in sealed polyethylene bags. The dust samples were
collected after the completion of PM sampling at the same sites.
They were swept carefully using a nylon brush and collected
into an aluminum foil pocket placed inside a Zip-locked bag.
Prior to use, the brush was rinsed with distilled water followed
by n-hexane. Large pieces of debris (e.g., hair, resin powder)
were manually removed from the dust samples by tweezers.
The samples were further sieved and stored at 20C before
analysis.
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The samples (dust, crushed TV components: 0.2 g, respectively) were digested according to USEPA method 3052
with modification. The samples were soaked with HNO 3
(9 mL, 69%), HF (3 mL, 40%) and H 2O2 (1 mL, 30%) in
PTFE-TFM vessels for 12 hr. Then, the mixtures were
heated progressively to 180C with a microwave digestion
instrument (Ethos A, Milestone). After cooling down the
vessels for 1 hr, the solutions were evaporated to near
dryness and transferred with water to 25 mL volumetric
flasks. Concentrations of Cu, Zn, Pb, Cd, Cr and Ni were
determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) with a Varian 710-ES device. The
instrumental conditions were set as follows: RF generator
power, 1.20 kW; plasma argon flow rate, 15 L/min; auxiliary argon flow rate, 1.5 L/min; and nebulizer pressure,
0.2 MPa.
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Raw material
warehouse
(P, D)
Other process
Other process
Drilling
Milling (P, D)
Lamination (P, D)
Profile (P, D)
Other process
Raw material
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PCB product
Fig. 1 Production flow of the PCB plant and the samples obtained. P: particle samples; D: dust samples.
Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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ADDing
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HQ
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HI
ADD
RfD
HQ i:
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The hazard index (HI) is the sum of HQ. If the HQ < 1, then
non-carcinogenic effects are impossible. If the HQ 1, adverse
health effect might likely appear. If the HQ > 10, then adverse
a high chronic risk exists (Leung et al., 2008).
Because reference values of carcinogenic risk through
ingestion and dermal exposure were not given by the US
EPA, in this study, we confine ourselves to the case of the
carcinogenic risk of heavy metals (Ni, Cr and Cd) resulting
from inhalation (Ferreira-Baptista and De Migue, 2005). The
lifetime average daily dose (LADD) was calculated and
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If the value of health risk falls within the safe range (106104),
then the contamination likely does not create a carcinogenic
risk (US EPA, 2011). Appendix Tables S1 and S2 present the
definitions and values of the exposure parameters used in
this study.
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LADDinh ADDinh=7
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1.4. QA/QC
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Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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0
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2
0
Cut lamination
PM2.5% = 6.00%
PM10% = 16.43%
D(4,3) = 41.53 m
Drilling
PM2.5% = 5.59%
PM10% = 14.22%
D(4,3) = 47.83 m
Milling
PM2.5% = 6.94%
PM10% = 16.94%
D(4,3) = 32.76 m
Lamination
PM2.5% = 8.42%
PM10% = 24.28%
D(4,3) = 31.23 m
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2
0
PM2.5% = 10.72%
PM10% = 26.15%
D(4,3) = 44.11 m
Percentage (%)
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0
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6 Profile
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2
0
0.01
1
10
Particle diameter (m)
100
PM2.5% = 7.00%
PM10% = 18.17%
D(4,3) = 37.37 m
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For workers in the workshops, PM10 and PM2.5 were the main
contaminants, suggesting that wearing a mask during working hours can obviously reduce the harmful health impacts of
particulate matter. According to the previous study showing
that the concentration of PM10 was 202.0 g/m3 (in the safe
range) in a typical PCB recycling workshop (US EPA, 1997), the
health risk of fine particulate matter to workers would be
reduced if each recycling production line was located in a
separate workshop and the physical part of each production
line could be isolated from one another by applying acoustical
hoods to reduce particle exposure. Considering that PM2.5
have a longer residence time and greater health hazards,
more advanced filter materials should be applied to the
dust-removal equipment to have a significant filtration
efficiency for fine particles (below 2.5 m diameter).
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off-site were 106.3, 90.0 and 50.2 g/m3, respectively, and the
concentrations of TSP, PM10 and PM2.5 in the workshops
ranged from 36.1 to 365.3, from 27.1 to 289.8 and from 22.1 to
212.3 g/m3, respectively. According to the Air Quality Standard of China (PM10 250 g/m3, PM2.5 75 g/m3, as shown
in Fig. 4), the off-site met the standard very well, suggesting
that the air quality outside the workshop building was
healthy. Most workshops qualified, except the Profile (for
PM10 and PM2.5) and Raw material warehouse (for PM2.5),
which indicated a mild degree of pollution. As the automatic
lines were under the running and non-running state, the
differences in TSP, PM10 and PM2.5 between the workshops
and off-site (Appendix Table S3) suggested that the industrial
art in these workshops made a considerable contribution to
the increase in particle concentration, reflected in three
aspects as follows: (1) During multiple scraping and separation processes, mutual collision and friction between the
coarse particles would inevitably produce fine particles
(below 10 m diameter), (2) the sectional high temperature
was one of the non-ignorable factors that generated aerosols.
(3) Fine particles would diffuse from the surface of the ground
into the ambient air of the workshop because of the vibration
generated by the equipment.
Furthermore, it was readily noticed that in Cut Lamination,
Drilling, Milling and Lamination, the mass concentrations of
TSP, PM10 and PM2.5 were very low, even lower than the off-site
(Fig. 4). This was because the dust-removal equipment was
applied in Cut Lamination, Drilling and Milling because the
industrial art in the three houses could create a large amount of
dust and/or particles if there were no dust-removal equipment.
For Lamination, because the industrial art in the house was a
wet process, the number of particles in air was settled and dust
on the ground could not be suspended.
The mean proportions of PM10 to TSP and PM2.5 to PM10 in
the workshops were 0.70 (ranged from 0.46 to 0.97) and 0.71
(ranged from 0.52 to 0.92), respectively. It is suggested that
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Fig. 2 Particle sizes of six dust samples collected from different PCB production processes.
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Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 4 ) XX XXXX
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sp1
Particle matter
sp1
sp2
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Glass cellulosic
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Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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PM2.5
PM10
TSP
Off-site
Recycling warehouse
Profile
Lamination
Milling
Drilling
Cut Lamination
Frozen warehouse
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200
Concentration (g/m3)
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by Lamination, Cut Lamination, Profile, Raw material warehouse and Drilling (Appendix Table S4). This result was
mainly due to the difference among these different industrial
arts and the variations among these semi-finished PCB
products disposed by these different industrial arts.
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Fig. 4 Mean concentration of PM2.5, PM10 and TSP at different sampling points.
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Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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10
0.5
5
0
2.5
2.0
1.5
Recycling
warehouse
2.5
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2.0
1.5
1.0
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1.0
Cd
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0.00
0.0
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0.04
C
Milling Lamination Profile
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Raw
Frozen
Cut
Drilling
material warehouse lamination
warehouse
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2
1.0
Ni concentration (mg/g)
Ni
0.0
Cr
0.0
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3.0
0.0
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Pb concentration (mg/g)
Pb
25
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Frozen
Cut
Drilling
material warehouse lamination
warehouse
Recycling
warehouse
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1.0
1.0
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10
1.5
2.0
450
2.5
20
Zn concentration (mg/g)
3.0
30
Zn
Cr concentration (mg/g)
3.5
2.0
600
Cd concentration (mg/g)
Cu concentration (mg/g)
4.0
40
4.5
Cu
PM2.5
PM10
TSP
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0.0
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Fig. 5 Mass concentration of six heavy metals (Cu, Zn, Pb, Cr, Ni and Cd) in TSP, PM10 and PM2.5 sampled at different points.
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The LADD and the risk caused by Cr, Ni and Cd via inhalation
are shown in Table 2. It can be seen that the carcinogenic risks
for Cr were all above 106 and ranged from 3.70 105 to
1.60 103. Alternatively, the carcinogenic risks for Ni and Cd
were almost lower than 106. Any cancer risk less than the
threshold value of 106 is considered negligible by the US EPA.
From these results, we could see that the lifetime cancer risk
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t1:1
t1:3
t1:2
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3. Conclusions
This study was conducted to investigate the actual occurrence
of six heavy metal (Cu, Zn, Pb, Cr, Ni and Cd) contaminants in
environmental samples from PCB production. For the environmental samples, heavy metal concentrations in dust and PM10
Table 1 Mass concentration of Cu, Zn, Pb, Cr, Ni and Cd in workshop dust.
t1:4
Sampling site
Cu (mg/g)
Zn (mg/g)
Pb (mg/g)
Cr (mg/g)
Ni (mg/g)
t1:5
t1:6
t1:7
t1:8
t1:9
t1:10
7.88
18.23
6.54
56.31
22.74
8.45
2.06
0.98
1.78
0.77
4.47
1.25
0.35
0.26
0.42
0.40
0.49
0.47
1.35
0.44
1.59
0.72
1.04
0.39
0.20
0.18
0.25
0.13
0.36
0.41
Cd (mg/g)
0.056
0.036
0.023
0.045
n.d.
n.d.
Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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Cut Lamination
10
0.1
0.1
Profile
0.01
1E-3
1E-3
1E-4
Cu
Zn
Pb
Cr
Ni
1E-4
Cd
Cu
Zn
Pb
1
0.1
HI
0.1
0.01
1E-3
Zn
Pb
Cr
Ni
1E-4
Cd
Cu
Zn
Pb
Cr
Ni
Cd
Cu
1E-5
Cd
1E-3
1E-4
Ni
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0.01
Cr
10
10
0.01
HQderm
Lamination
HQinh
HQinh
Milling
Drilling
10
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Fig. 6 Hazard quotients and hazard index for non-carcinogenic metals in different sampling points.
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Table 2 Lifetime average daily doses and risk for each carcinogenic metal via inhalation in the automatic workshop.
t2:3
t2:2
t2:4
t2:5
t2:6
t2:7
t2:8
t2:9
t2:10
t2:11
t2:12
t2:13
t2:14
t2:15
t2:16
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4. Uncited references
LADDinh (mg/(kgday))
Risk
LADDinh (mg/(kgday))
Risk
LADDinh (mg/(kgday))
Risk
LADDinh (mg/(kgday))
Risk
LADDinh (mg/(kgday))
Risk
LADDinh(mg/(kgday))
Risk
Cr-cancer
Ni-cancer
Cd-cancer
3.80E 05
1.60E 03
2.00E 06
8.41E 05
1.17E 06
4.91E 05
1.88E 06
7.90E 05
1.01E 05
4.23E 04
8.81E 07
3.70E 05
1.06E 06
8.94E 07
1.08E 06
9.04E 07
4.70E 07
3.95E 07
5.54E 07
4.65E 07
1.58E 06
1.33E 06
1.08E 06
9.08E 07
6.08E 08
3.83E 07
2.03E 07
1.28E 06
Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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Please cite this article as: Zhou, P., et al., PM2.5, PM10 and health risk assessment of heavy metals in a typical printed circuit noards
manufacturing workshop, J. Environ. Sci. (2014), http://dx.doi.org/10.1016/j.jes.2014.08.003
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