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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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PM2.5, PM10 and health risk assessment of heavy metals in a


typical printed circuit noards manufacturing workshop

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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Received 13 November 2013

the object of this study. During PCB processing, fine particulate matter and heavy metals

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Revised 2 February 2014

(Cu, Zn, Pb, Cr, Cd and Ni) will be released into the air and dust, which then impact workers'

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Accepted 28 February 2014

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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technology is advanced from the perspective of environmental protection in the waste

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PCB's recycling industry.

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2014 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.

Introduction

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With the development of the electronic industry and information


technology, the production of electrical and electronic equipment (EEE) has been increasing rapidly in recent decades (TPCA,
2004). As an essential part in EEE, Printed Circuit Board (PCB)
manufacturing has been growing rapidly as a matter of course.
According to a relevant survey report, the global production and
market of PCBs were estimated to be approximately 300 106 m2
and 45 billion dollars in 2008, where the East Asia region

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Published by Elsevier B.V.

contributed to over 80% of the total production value (TPCA,


2004). The average growth rate of PCB production has risen by
8.7% in recent years, and data were supposedly much higher in
mainland China, reaching up to 14.4% (Li et al., 2007).
A PCB consists of a non-conducting substrate, typically
fiberglass with epoxy resin, upon which a conductive pattern or
circuitry is formed. Copper is the most prevalent conductor,
although nickel and tinlead, due to their excellent electric
conductivity and thermal conductibility properties (Bykbay et
al., 2010). As the previous study reported, the compositions of
copper, lead and nickel in the final PCB product by weight are

Corresponding author. Email: kuangfeilin@ecust.edu.cn (Kuangfei Lin).

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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1.1. PCB manufacturing plant and sample descriptions

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This study was conducted on a typical PCB manufacturing


plant in Eastern China with a monthly PCB output of
46,000 m2. The production process, commonplace to all PCB
manufacture, is described as follows. First, several layers of
epoxy resin-based substrates are laminated with copper foils
to create multilayer boards. Photographic tools are utilized to
transfer the circuit design to the substrates. Holes are drilled
through the substrates to establish electrical paths according
to the circuit design, and copper coats are plated to make the
holes conductive. Then, unwanted copper is etched to expose
the desired copper pattern. After appropriate cleaning, electrical testing and final inspection, the production of a PCB is
accomplished. The main production processes that could
produce a large number of particles are shown in Fig. 1,

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1.2. Sample collection

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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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1.3. Digestion and analysis of heavy metals

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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)

Cut lamination (P, D)

Other process

Other process

Drilling

Milling (P, D)

Lamination (P, D)

Profile (P, D)

Other process

Raw material

Q1

including raw material warehousing, cut lamination, milling,


drilling, lamination and profiling. Samples were collected
along these processes and classified into the following
categories: PM and dust samples.

approximately 10%20%, 1%5% and 1%3%, respectively (Veit et


al., 2006). Those substances were consumed in large quantities
due to the huge demand for PCB product all over the world. On the
other hand, there are numerous steps required (including board
preparation, drilling, image transfer, etching, plating and others)
to produce the final product (LaDou, 2006; Lam et al., 2011). During
these processes, the powder (especially fine particulate matter)
will be released into the surrounding environment, which can
pass through the alveolus and reach parts of the body by the
circulatory system; the quantity of PM2.5 constitutes 96% of all
particles deposited in the lung parenchyma (Churg and Brauer,
1997). Furthermore, heavy metals (such as Cu, Cr, Cd, Ni and Pb)
could be adhered on the particulate matter, which will cause
various health problems for workers in the workshops and
residents around the factory (Gullett et al., 2007; Bi et al., 2010).
Therefore, it is important to focus on the potential release of these
substances into the environment (Chinese National Standard; US
EPA, 2000).
In current publications, there is no comprehensive research
focus on the content of PM2.5 and PM10 or a health risk
assessment for heavy metals during the PCB production process.
Meanwhile, most researchers have focused on the health risk
assessment of total suspended particle (TSP) and PM10, but there
is a lack of systematic studies on heavy metals in PM2.5, which
poses a greater health risk to workers. Therefore, it was valuable
for us to monitor a series of data sources on the representative
PCB production process; these data would be significant for the
State Environmental Protection Department to develop relevant
environmental standards and for companies to make the PCB
production process more environmentally friendly. The major
objective of this work was to study the distribution characteristics of heavy metals in the workshops and to estimate chronic
risk to the workers.

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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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A procedure blank, a standard spiked blank and duplicate


samples were run with each batch of samples to ensure
accuracy and reproducibility. No detectable target substances were found in the blanks. The recovery for all
measured metals ranged from 80.5% to 96.8%, which was
acceptable for certification.

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1.5. Health risk assessment of heavy metals

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Fine particulate matter, especially PM2.5, will cause health


risks to workers and residents mainly in three ways: ingestion, inhalation and dermal contact. This study adopted
health risk assessment models from the US EPA to evaluate
health risks of heavy metals surrounding the workshops and
factory. The average daily dose through ingestion (ADDing),
inhalation (ADDinh) and dermal contact (ADDderm) can be
calculated as follows (USEPA/600/P-95/002F, 1997):

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ADDing

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C inh  InhR  EDF


:
ADDinh
BW

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where, Cing is the concentration of the pollutant absorbed by


inhalation, and Cderm is the concentration of the pollutant
absorbed through the skin.
A hazard quotient (HQ) indicates the non-carcinogenic
risks of a single contaminant, compared to the hazard index
(HI), which represents the total non-carcinogenic risks of
different pollutants through the above-mentioned three ways.
The formulas for determining the HQ and HI are as follows
(USEPA/600/P-95/002F, 1997):

HQ

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C derm  SA  SL  ABS  EDF


BW

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Average daily dose absorbed through the skin (ADDderm) is


computed by
ADDderm

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C ing  IngR  EDF


BW

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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

Risk LADD  SF:

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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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2. Results and discussion

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2.1. Properties of particle matter and dust

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The Scanning Electron Microscope (SEM) observation of the


particle matter and dust was conducted using U9320A 8500
and the microshapes of samples collected form the Drilling
shop were shown in Appendix Fig. S1. As expected, significant variations in shapes and size were observed among
these samples. The particle size decreased in the following
order: Dust > TSP > PM10 > PM2.5. Moreover, the particle size
distributions of six dust samples ranged from 0.3 to 750 m,
as seen in Fig. 2. The composition of PM2.5 and PM10 in these
dust ranged from 5.59% to 10.72% and form 14.22% to 26.15%,
respectively. The average diameters (D(4,3)) decreased in the
following order: Drilling (47.83 m) > Raw material warehouse
(44.11 m) > Cut lamination (41.53 m) > Profile (37.37 m) >
Milling (32.76 m) > Lamination (31.23 m). These differences
were mainly due to the different manufacturing process.
The Transmission Electron Microscope (TEM) observation
of the Particle matter was conducted using JEM-2010HT and
the microshapes are shown in Fig. 3. From the result, we can
obviously see different compositions between sp1 and
sp2. Except from Cu and Sn, the sp1 contains some
non-metallic element, such as Si, C, O, and Cl. This indicated
that the sp1 particle was the nature particulate matter in
the atmosphere. However, only some metallic elements
(such as Cu, Zn, Pb, Cr) were observed in sp2. This suggests
that the SP2 particle was artificial particle rather than the
nature particulate matter. This further suggested that fine
particles might release to the surrounding atmosphere of
those processes due to mechanical and thermal stress on
board and expose workers engaged to heavy metals with
harmful health effects via inhalation and ingestion.

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2.2. Assessment of TSP, PM10 and PM2.5 in the workshops

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2.2.1. Mass concentrations of TSP, PM10 and PM2.5

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The mass concentrations of TSP (total suspended particles),


PM10 (particles below 10 m diameter) and PM2.5 (particles
below 2.5 m diameter) at the nine sampling points, containing eight workshops and one contrast site, were monitored
from December 2011 to February 2012. As shown in Appendix
Table S3, the concentrations of TSP, PM10 and PM2.5 in the

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LADDinh ADDinh=7

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multiplied by the slope factor (SF) to produce the cancer 207


risk level as follows:
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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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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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PM2.5% = 10.72%
PM10% = 26.15%
D(4,3) = 44.11 m

Percentage (%)

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Raw material warehouse

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6 Profile
4
2
0
0.01

1
10
Particle diameter (m)

100

PM2.5% = 7.00%
PM10% = 18.17%
D(4,3) = 37.37 m

1000

0.1

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2
0

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2.2.2. Management strategy

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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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the air in the workshops is dominated by fine particles and


might pose health risks to the workers. The difference in the
proportion between these workshops was most likely due to
different industrial art. Moreover, it was expected that in the
workshops, the PM10 concentrations would correlate relatively
well with TSP concentrations and that PM2.5 concentrations
would correlate relatively well with PM10 concentrations, with
the correlation coefficients R2 = 0.84 (P < 0.05) and R2 = 0.95
(P < 0.01), respectively.

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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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2.3. Distribution characteristics of heavy metals in TSP, PM10 319


and PM2.5
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The average concentration of heavy metals (Cu, Zn, Pb, Cr, Ni
and Cd) in particulate matter and the ratios of metal
concentrations in PM2.5 to those in PM10 in the automatic
workshops are shown in Fig. 5 and Appendix Table S4. Almost
every heavy metal was detected in all of the particle samples
collected from these workshops except Cd. For each

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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sp2

sp1
Particle matter

sp1

sp2

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Glass cellulosic

Fig. 3 Transmission electron microscope (TEM) of particle matter samples.

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workshop, it was obvious that Zn was the most enriched


metal in TSP, followed by Cu > Pb (Cr) > Ni > Cd, and the
same trend was found for PM10 and PM2.5. This result was
different from the composition of the five heavy metals of
raw materials in which Cu was the largest, followed by
Pb > Zn > Cr > Ni > Cd (Bykbay et al., 2010). This result
indicated that Zn was most easily released into the
suspended particles. Moreover, the ratios of the concentration in PM2.5 to that in PM10 for different metals were also
varied. Taking the Raw material warehouse as an example,
the ratio of the concentration in PM2.5 to that in PM10 varied
from 0.71 for Cd to 4.35 for Ni. Furthermore, for each metal,
the concentration and the ratio of the concentration in PM2.5
to that in PM10 varied largely between these workshops. For
example, the concentration of Cu in the TSP samples varied

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from 3.26 mg/g in the Lamination to 42.23 mg/g in the


Recycling warehouse, and the ratio of the concentration in
PM2.5 to that in PM10 varied from 0.95 in Milling to 4.46 in
Lamination. This finding indicated that the escape capability
of each heavy metal varied in the different workshops
because the environmental conditions of the workshops
varied and the different-sized particles had different adsorptive capacities for each heavy metal (Xue et al., 2011).
The correlations (R2) of metal concentrations in PM2.5 and
PM10 were 0.349 for Cu, 0.898 for Zn (p < 0.01), 0.965 for Pb
(p < 0.01), 0.850 for Cd (p < 0.05), 0.004 for Ni and 0.897 for Cd
(p < 0.01), respectively. It was not surprising that the metal
concentrations in PM2.5 were comparable with those in PM10
because PM2.5 and PM10 were homologous. However, Cu and
Ni were not comparable within PM2.5 and PM10. For Cu, it may

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

100

200
Concentration (g/m3)

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Raw material warehouse

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2.4. Distribution characteristics of heavy metals in dust

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The average concentrations of six heavy metals (Cu, Zn, Pb,


Cr, Ni and Cd) in the automatic workshop dust are shown in
Table 1. All of the six heavy metals were detected in all of the
dust samples collected from these workshops except Cd. This
finding demonstrates that toxic heavy metals were released
into dust during the PCB production process. As Table 1
shows, Cu (which ranged from 6.54 to 56.31 mg/g) was the
most enriched metal in the dust samples, followed by Zn, Pb,
Cr, Ni and Cd, with the corresponding concentrations ranging
from 0.77 to 4.47, 0.26 to 0.49, 0.39 to 1.59, 0.13 to 0.41 and nd
to 0.056 mg/g, respectively. This result was not unexpected
because Cu is one of the main raw materials, due to its good
electric conductivity and cost performance (Bykbay et al.,
2010; Veit et al., 2006). The content of Cd was the least among
the six metals in the present study. This observation was
consistent with the study of the production line for recycling
Waste Printed Circuit Boards. However, the content of Pb in
this study was 5 to 10 times lower than Xue's study, mainly
because of the product time of PCB and the statute RoHS. In
this study, the product time was at the end of 2006, which is
the time when RoHS became effective in Europe. However,
the object of Xue et al.'s study was the Production Line for
Recycling Waste Printed Circuit Boards (WPCBs), where the
WPCBs were a majority product before 2006 (Xue et al., 2011).
Furthermore, RoHS set a limit of 1000 mg/kg for Pb content in
the PCB product.
Among these workshops, the content of the identical
heavy metals in dust greatly varied. Taking Cu as an example,
the most enriched dust was collected from Milling, followed

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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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2.5. Heavy metal risk assessment

396

360

be because some copper particles blended randomly in the


suspended particles. For Ni, it may be because there was no
release of Ni during the process of PCB manufacturing; the
detected concentration of Ni was the background value.

358

357

Fig. 4 Mean concentration of PM2.5, PM10 and TSP at different sampling points.

392
393
394
395

2.5.1. Risk assessment for non-carcinogenic metals in the 397


workshop
398
The hazards of heavy metals for human health are well known.
Considering that the concentrations of heavy metals in dust and
particle samples were above the safe range in the automatic
workshop, health risk assessment appears to be quite necessary.
The model of health risk assessment of US EPA was applied to
evaluate the hazard indexes of Cu, Zn, Pb, Cr, Ni and Cd in dust
and PM10 samples. The results of ADD are shown in Appendix
Table S5, and the values of hazard quotients and hazard indexes
of each non-carcinogenic metal in the workshop are shown in
Fig. 6 and Appendix Table S6. For inhalation, the hazard
quotients (HQs) of the heavy metals showed a sequential order
as Cr > Ni > Pb > Zn > Cu > Cd. It was readily known that the
HQs of Cr were all above 0.1 but below 1. The HQs of the other
heavy metals were all below 0.1. For ingestion, the HQs of the
heavy metals showed a sequential order as Cu > Cr > Pb > Cd >
Ni > Zn and all the HQ values were below 1. For dermal contact,
the HQs of the heavy metals showed a sequential order as
Cr > Cd > Cu >Pb > Ni > Zn and all of the HQ values were below
0.1. The HQs for all the six heavy metals (Cu, Zn, Pb, Cr, Ni and
Cd) were less than 1, which suggested that noncancerous effects
were unlikely. Among the six heavy metals, the HQ for Cr
contacted through ingestion was the highest. The possible
reason for this result was that Cr had a high concentration in
WPCBs and could be released more easily during processing. For
the three main exposure routes, ingestion of dust and inhalation
resulted in a greater health risk to workers compared to dermal

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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401
402
403
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408
409
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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

20
15

1.0

10
0.5
5
0

2.5

2.0
1.5

Recycling
warehouse

2.5

2
1

2.0
1.5
1.0
0.5

1.0
Cd

0.08

0.8

0.4

0.02

0.2

0.00

Ratio of Ni concentration in PM2.5 and PM10

0.0

0.10

0.04

C
Milling Lamination Profile

0.6

Raw
Frozen
Cut
Drilling
material warehouse lamination
warehouse

0.5

3.0

0.06

2
1.0

Ratio of Ni concentration in PM2.5 and PM10

Ni concentration (mg/g)

Ni

0.0

Cr

0.0
5

3.0

0.0
3.5

Ratio of Ni concentration in PM2.5 and PM10

1.5

0
5

Pb concentration (mg/g)

Pb
25

0.5

Raw
Frozen
Cut
Drilling
material warehouse lamination
warehouse

Milling Lamination Profile

Recycling
warehouse

Ratio of Ni concentration in PM2.5 and PM10

0.0
2.0

0
30

150

0.5

1.0

1.0

300

R
O

1.5
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

Ratio of Ni concentration in PM2.5 and PM10

4.5

Cu

PM2.5

PM10

Ratio of Ni concentration in PM2.5 and PM10

TSP
5.0

50

0.0

425

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C
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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.

contact. It is concluded that different exposure pathways


present different levels of risk for each metal.

427

2.5.2. Carcinogenic metal risk assessment

428

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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434

t1:1
t1:3
t1:2

426

of Cr obviously exceeded the threshold and may have a cancer 435


risk for workers and residents.
436

437
438

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

Raw material warehouse


Cut Lamination
Drilling
Milling
Lamination
Profile

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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J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 4 ) XXX XXX

Raw meterial warehouse

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

R
O

0.01

Cr

10

10

0.01

HQderm

Lamination

HQinh

HQinh

Milling

Drilling

10

449
450
451
452
453
454
455
456

t2:1

448

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445

samples were on the high end of reported values worldwide,


suggesting that PCB production is a remarkable heavy metal
source in the indoor environment. Additionally, the estimated
worker exposures were significantly higher in some production
processes, including the raw material warehouse and lamination. Exposure through dust contributes the majority of total
exposure within most of the processes. Although different
exposure parameters may lead to variability in exposure
results, our estimation provides a referable database for further
study on cleaner production and occupational hazards. According to our estimation, protection measures such as wearing a
dust mask and reducing exposed body area are more practical
strategies for lowering occupational exposure to heavy metals
in PCB production.

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Fig. 6 Hazard quotients and hazard index for non-carcinogenic metals in different sampling points.

Chinese National Standard, 2009


U.S. Environment Protection Agency, 2000
Xue et al., 2012

459

Acknowledgments

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462

This work was supported by the National Natural Science


Foundation of China (No. 40901148), the Science and Technology Committee Research Program of Shanghai (No.
12DZ0502700), the National Environmental Protection Public

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461

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

Raw material warehouse


Cut lamination
Drilling
Milling
Lamination
Profile

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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Appendix A. Supplementary data

476

Supplementary data to this article can be found online at


http://dx.doi.org/10.1016/j.jes.2014.08.003.

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8

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Welfare Science and Technology Research Program of China


(No. 201309047), the National Natural Science Foundation of
China (No. 41001316) and the Fundamental Research Funds
for the Central Universities (No. WB1214059). We also appreciate the anonymous referees for their helpful comments on
this paper.

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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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