Environmental Pollution 157 (2009) 1365–1372

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

The impact of semiconductor, electronics and optoelectronic industries on

downstream perfluorinated chemical contamination in Taiwanese rivers
Angela Yu-Chen Lin*, Sri Chandana Panchangam, Chao-Chun Lo
National Taiwan University, Graduate Institute of Environmental Engineering, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan

The semiconductor, electronics and optoelectronic industries are the primary source of PFC contamination in downstream aqueous environments.

a r t i c l e i n f o a b s t r a c t

Article history: This study provides the first evidence on the influence of the semiconductor and electronics industries
Received 1 September 2008 on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs,
Received in revised form including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs:
10 November 2008
PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic
Accepted 19 November 2008
industrial wastewaters and their receiving water bodies (Taiwan’s Keya, Touchien, and Xiaoli rivers).
PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However,
Keywords:
different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant
Perfluorinated chemicals
PFOA PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%).
PFOS The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA
Semiconductor and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest
Optoelectronics concentrations (up to 5.4 mg/L).
Photolithographic process Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Perfluorinated chemicals (PFCs) have been in ubiquitous
production and usage for more than half a century. Their hydro-
phobic and lipophobic properties make them an important
component of many common industrial and commercial applica-
tions, including stain repellents, corrosion inhibitors, surfactants,
fire-fighting foams, and photolithographic film (Giesy and Kannan,
2002). In the course of intentional use or unintended loss, PFCs are
released into the environment in sizable quantities (Prevedouros
et al., 2006; Skutlarek et al., 2006), and as a result, global presence
of PFCs is extremely pervasive. The PFCs have been found to be
stable at environmental conditions, and of them, perfluorooctanoic
acid (PFOA) and perfluorooctane sulfonate (PFOS) are especially
stable, can resist direct and indirect photolysis, and have hydrolytic
half-lives >41 years (Giesy et al., 2006). Given their resistance to
attenuation in natural environments, PFCs can be expected to
appear in various environmental matrices. In recent years,
a number of researchers have reported the presence of PFCs at
significant concentrations in the aquatic environment of several
countries, including Japan, the United States, Germany, and Italy
(Lien et al., 2008; Nakayama et al., 2007; Becker et al., 2008; Loos
* Corresponding author. Tel.: þ886 2 3366 3729; fax: þ886 2 2392 8830.
E-mail address: yuchenlin@ntu.edu.tw (A.Y.-C. Lin).
et al., 2008). PFCs have been found predominantly in the aqueous
environment, particularly in rivers and natural aquatic systems.
Significant amounts of PFOA and PFOS have been found in Japanese
river waters, at concentrations ranging from 7.9 to 110 ng/L and
<5.2 to 10 ng/L, respectively (Senthilkumar et al., 2007); in Japan’s
Yodo River basin’s surface water in particular, concentrations as
high as 123 ng/L (PFOS) and 2600 ng/L (PFOA) were recorded (Lien
et al., 2008). PFCs have even been found in drinking water at
a concentration of 598 ng/L, with PFOA comprising the majority
(519 ng/L) (Skutlarek et al., 2006).
Several PFCs have been detected in wastewater treatment plants
(WWTPs), with PFOA and PFOS being the predominant species,
ranging from tens to thousands of ng/L (Sinclair and Kannan, 2006;
Loganathan et al., 2007). Becker et al. (2008) showed a 20- to
30-fold increase of PFOA and PFOS concentrations in WWTP
effluents in Germany following the degradation of precursor PFCs.
Significant amounts of PFCs have also been seen in industrial
discharges, where reported concentrations were even higher than
in WWTPs; up to 0.38 mg/L (PFOS) and 6.57 mg/L (PFOA) were
detected in waters from Fallon Naval Air Station in the United States
due to aqueous fire-fighting foam (Schultz et al., 2004). Moreover,
high levels of PFCs (ng/L) have been measured in coastal seawaters
of Korea and attributed to industrialization (So et al., 2004). These
findings suggest that water bodies located near highly industrial-
ized zones are more prone to PFC contamination. The two PFC
classes of greatest concern from an environmental and health

0269-7491/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2008.11.033
1366 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372
perspective are the perfluoroalkyl sulfonates (PFAS, CF3(CF2)nSO 3)
and perfluoroalkyl carboxylates (PFCA, CF3(CF2)nCO
2 ). Among
members of these classes, PFOS and PFOA have drawn the most
attention because of their demonstrated abundance. PFOS has been
found to derive from perfluorooctane sulfonamides (N-ethyl per-
fluorooctane sulfonaminoethanol and N-ethyl perfluorooctane
sulfonamide) (Xu et al., 2004; Boulanger et al., 2005), and PFOA
from fluorotelomer alcohols (Wang et al., 2005; Prevedouros et al.,
2006) via degradative processes such as atmospheric oxidation,
biodegradation, and biotransformation. Between the two, PFOS is
more abundant in biota due to its higher bio-accumulation
potential (Kannan et al., 2005; Jensen and Leffers, 2008). Other
lower-profile PFCs which occur commonly, albeit in lower
concentrations, include perfluorobutane sulfonate (PFBS), per-
fluorohexane sulfonate (PFHxS), perfluorooctane sulfonamide
(PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid
(PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid
(PFDA), and perfluoroundecanoic acid (PFUnA), and at even
lower levels, perfluorododecanoic acid (PFDoA) and per-
fluorotetradecanoic acid (PFTA) (Loganathan et al., 2007; Nakayama
et al., 2007; So et al., 2007). When large concentrations of these
other PFCs have been found, however, the most common expla-
nation for their occurrence is the postulation of a point source of
the chemicals. For example, So et al. (2007) found an abundance of
PFBS contributing 22.9–26.1% of the total PFC load, indicating
a possible PFBS source in water near Nanjing, China. Similarly,
perfluorohexane sulfonate (PFHxS) has been measured at concen-
trations approaching those of PFOA and PFOS in effluents in the
state of New York, indicating the specific introduction of PFHxS into
WWTPs through domestic or industrial influences (Sinclair and
Kannan, 2006).
In recognition of the potential negative health effects of wide-
spread PFC contamination in the aquatic compartment, guidelines
for acceptable PFC levels in drinking water in the U.S. have been
issued by local governmental authorities (Minnesota Department
of Health, 2007; State of New Jersey Department of Environmental
Protection, 2007). However, despite findings of global contamina-
tion and a resultant ban on PFOS in most consumer products
(European Commission, 2006), the semiconductor and electronics
industries continue to use this chemical. Moreover, it is likely that
PFOS will be included in the Stockholm Convention’s Persistent
Organic Pollutants list due to its persistent, bioaccumulative, and
toxic characteristics (Swedish chemicals inspectorate (Keml), 2006;
Working Draft Risk Profile of Perfluorooctane Sulfonate
(PFOS), 2006).
Taiwan is undergoing rapid industrialization and is already
home to a world-class semiconductor industry. The objective of this
study was to develop an analytical method to identify and describe
the concentration profiles of the ten PFCs known to exist in aqueous
environments. We have also correlated the presence of semi-
conductor, electronics, and optoelectronics industries to the
distribution of PFCs in the downstream rivers. To the best of our
knowledge, this study is the first to report PFC concentrations in
effluents from semiconductor, electronics, and optoelectronics
industrial facilities and the influence of these toxins on receiving
river waters.
2. Materials and methods
2.1. Chemicals and standards
LC–MS grade methanol was purchased from J.T. Baker (Phillipsburg, PA, USA).
Ammonium acetate, perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid
(PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), per-
fluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were
purchased from Sigma Aldrich (St. Louis, MO, USA). Perfluorobutane sulfonate
tetrabutylammonium (PFBS), perfluorohexanoic acid (PFHxA), tridecafluorohexane-
1-sulfonic acid potassium salt (PFHxS), and potassium perfluorooctane sulfonate
(PFOS) were purchased from Fluka (Buchs, Switzerland). 13C8-Perfluorooctanoic acid
(13C8-PFOA) was purchased from Cambridge Isotope Laboratories (Andover, MA,
USA). All chemical standards were of purity >97.20%. Table 1 lists the ten target PFCs
with their corresponding chemical formulas and structures.
Individual stock standard solutions were prepared on a weight basis in meth-
anol and stored in amber glass bottles at 4  C. Standard mixtures at different
concentrations were prepared by appropriate dilution of the stock solutions before
each analytical run.
2.2. Sample collection and preparation
Grab samples (500 mL) were collected from each sampling site in polypropylene
bottles (rinsed with methanol) and stored in ice-packed coolers. Water samples
were collected at 24 sampling sites, including waters from a semiconductor fabri-
cation plant (which will be referred to as SEM-A) (3 sampling sites), an electronics/
optoelectronics fabrication plant (here denoted as ELE/OPTO-A) (18 sites), and
surface river waters (3 sites). Fig. 1 shows a map of the region with the three river
sampling sites indicated. These three rivers are the receiving bodies of discharge
from SEM-A, ELE/OPTO-A, and other optoelectronic factories. The Touchien River,
located downstream of ELE/OPTO-A, is 23 km long with a flow rate of 23.24 m3/s and
serves a population of 790,000. The Xiaoli River is 16 km long with a flow rate of
0.67 m3/s and serves a population of 38,000. The Keya River is 24 km long, flows at
1.93 m3/s, and serves as wastewater drainage. For each site, triplicate samples were
taken, and all three samples underwent analysis.
All water samples were vacuum-filtered through 0.45 mm and 0.22 mm cellulose
acetate membrane filters and stored at 4  C until analysis. Oasis HLB cartridges
(Waters, Milford, MA, USA) with 200 mg 6 mL hydrophilic–lipophilic balance were
employed for solid phase extraction (SPE), using sample volumes of 400 mL.
SPE cartridges were preconditioned with 6 mL of methanol and 6 mL of Milli-Q
water. 13C8-PFOA (employed as a surrogate) was added to aliquots of 400 mL water
samples. Samples were loaded into the cartridges with a flow rate of 3–6 mL/min.
After sample passage, the cartridges were rinsed with 6 mL Milli-Q water, followed
by 6 mL of 30% aqueous methanol, and dried by nitrogen stream for 5 min. After
drying, the analytes were eluted twice with 3 mL of methanol. The eluates were
collected, evaporated to dryness with nitrogen stream, and reconstituted to 0.4 mL
with 50% aqueous methanol. The final solutions were filtered through a 0.45 mm
nylon membrane filter before liquid chromatography/tandem mass spectrometry
(HPLC–MS/MS) analysis.
2.3. LC–ESI–tandem MS analysis
Chromatographic separation of analytes was performed using an Agilent 1200
module (Agilent, Palo Alto, CA, USA) equipped with a ZORBAX Eclipse XDB-C18
column (150  4.6 mm, 5 mm). A binary gradient was used. The elution program,
which maintained a flow rate of 1.0 mL/min, started with 63% of water (containing
1 mM ammonium acetate) and went up to 95% of methanol (containing 1 mM
ammonium acetate). After 7 min, all target PFCs were separated and eluted. The
sample injection volume was 20 mL, and the autosampler was operated at room
temperature.
Mass spectrometric measurements were carried out on a Sciex API 4000
(Applied Biosystems, Foster City, CA, USA) equipped with an electrospray ionization
(ESI) interface. Analyses were performed in negative mode for all perfluorinated
compounds. Ions were acquired in multiple reaction monitoring (MRM) mode with
a dwell time of 30 ms and unit mass resolution on both mass analyzers. The
following mass spectrometer conditions were used: ion spray voltage 4.5 kV;
curtain gas, nebulizer gas, turbo gas at 10 L/h, 50 L/h, and 40 L/h, respectively;
heated capillary temperature 500  C; collisionally activated dissociation 5. After
selecting the precursor ions, product ions were determined and optimized with four
key parameters: declustering potential, entrance potential, collision energy, and
collision cell exit potential.
2.4. Detection, quantification, and quality control
Quantification of pharmaceuticals was performed via HPLC–MS/MS with MRM,
using the two highest characteristic precursor ion/product ion transition pairs.
Compounds were identified using the LC retention time 30 s of the retention time
of a standard.
Percent recoveries were determined by spiking Milli-Q and river waters with the
5 and 50 ng/L target analytes and comparing their concentrations before and after
the SPE extraction. Accuracy and precision were determined by repeated intra-day
analysis of Milli-Q and river water samples (n ¼ 6) and were expressed as a relative
standard deviation (RSD). The standard calibration curve was constructed with
Milli-Q water spiking with perfluorinated compound standard solutions at 0.5, 1.0,
2.5, 5, 7.5, 10, 25, 50, and 75 mg/L. The linearity of calibration curves was estimated by
fitting a linear mode, least-squares regression analysis (y ¼ a þ bx) in the concen-
tration range studied. The method detection limits (MDLs) were determined with
the minimum concentration of analyte in the linear range and a signal-to-noise ratio
3:1 in DI water (Table 2). Compounds were quantified using the first MRM pair for
each compounds listed in Table 2.
 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372 1367

Table 1
A list of the perfluorinated chemicals (PFCs) investigated here.

Compounds Acronym MW Chemical formula CAS number Molecular Structure

Perfluoroalkyl sulfonate PFAS
O
CF 3(CF 2)2CF 2 S O
Perfluorobutyl sulfonate PFBS 299.21 C4F9SO3 29420-49-3
O

O
CF 3(CF 2)4CF 2 S O
Perfluorohexyl sulfonate PFHxS 399.22 C6F13SO3 3871-99-6
O

O
CF 3(CF 2)6CF 2 S O
Perfluorooctyl sulfonate PFOS 499.23 C8F17SO3 2795-39-3
O

Perfluoroalkyl carboxylates PFCA

O
C
Perfluorohexanoic acid PFHxA 314.05 C6HF11O2 307-24-4
CF3(CF2)3CF2 OH

O
C
Perfluoroheptanoic acid PFHpA 364.06 C7HF13O2 375-85-9 OH
CF 3(CF 2) 4CF 2

O
C
Perfluorooctanoic acid PFOA 414.07 C8HF15O2 335-67-1
CF 3(CF 2) 5CF 2 OH

O
C
Perfluorononanoic acid PFNA 464.08 C9HF17O2 375-95-1
CF3(CF2)6CF2 OH

O
C
Perfluorodecanoic acid PFDA 514.09 C10HF19O2 335-76-2
CF 3(CF 2) 7CF 2 OH

O
C
Perfluoroundecanoic acid PFUnA 564.09 C11HF21O2 2058-94-8 OH
CF 3(CF 2) 8CF 2

O
C
Perfluorododecanoic acid PFDoA 614.1 C12HF23O2 307-55-1
CF3(CF 2)9CF2 OH

O
13 13 13
C8-Perfluorooctanoic acid C8-PFOA 422.06 C8HF15O2 C
CF 3(CF 2)5CF 2 OH
1368 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372

Fig. 1. Map of the sampling region.

3. Results and discussion
3.1. Quantification, method validation
A simple but sensitive LC–MS/MS method was used to quantify
three C4–C8 perfluoroalkyl sulfonates (PFASs) and seven C6–C12
perfluoroalkyl carboxylates (PFCAs) in various water sample
matrices. A total ion chromatogram of the ten targeted PFCs is
shown in Supplementary figure. Each compound was identified
with two MRM pairs (labeled) and quantified with the higher
intensity pair. DI water was found to have relatively high back-
ground PFC levels, and therefore, Milli-Q water was used as the test
Table 2
The perfluorinated chemicals (PFCs) investigated, their MRM pairs, recoveries in
Milli-Q and river waters, method detection limit (MDLs), and linearity.
matrix. Recoveries in both Milli-Q water and environmental
aqueous samples, method detection limits (MDLs), accuracies, and
precisions for intra- and inter-day data are presented in Table 2.
With the exception of PFBS and PFHxA, recoveries for both Milli-Q
and river waters were high and similar even at low PFC concen-
trations (5 ng/L), indicating an insignificant matrix effect on our
analysis of target PFCs in an environmental matrix. All recovery
experiments (including accuracy and precision tests) were
repeated at higher concentrations (50 ng/L: data not shown) with
higher recoveries achieved. The MDLs ranged from 0.05 to 0.24 ng/L
with linearity (coefficient of determination) >0.9946. Some of the
waste effluent samples were expected to have high PFC concen-
trations; therefore, direct injections into the HPLC–MS/MS (without
SPE) were performed, with resulting MDLs of 5 mg/L (PFDoA), 1 mg/L
(PFUnA, PFHpA, and PFOS), 0.5 mg/L (PFDA, PFNA, and PFOA), and
0.1 mg/L (remaining PFCs).

Compounds MRM Retention 5 ng/L (n ¼ 6) MDLs

(m/z) time (min) (ng/L)
3.2. PFC concentrations in semiconductor fabrication plant (SEM-A)
Milli-Q water River water waters: pure water, photolithographic process wastewaters, and
Recovery  RSD Recovery  RSD final waste effluents
SD (%) (%) SD (%) (%)
PFBS 299 > 80 3.29 46  5 9.8 14  1 8.4 0.05 PFC levels were determined for waters associated with a semi-
299 > 99 conductor fabrication plant (SEM-A), with varying concentrations
PFHxS 399 > 80 3.62 75  4 5.5 87  4 4.7 0.08
399 > 99
at each stage shown in Table 3. PFCs were analyzed in SEM-A pure
PFOS 499 > 80 4.06 69  5 7.9 102  5 4.4 0.25 waters (i.e. the pure water manufactured by the plant for plant use),
499 > 99 and all but two PFCs (PFHxA and PFUnA) were present at ng/L
PFHxA 313 > 269 3.47 30  2 7.5 24  7 30.2 0.10 levels. The concentration of PFOS was highest (36.70 ng/L), fol-
313 > 119
lowed by PFHxS (24.22 ng/L) and PFBS (5.74 ng/L). The concentra-
PFHpA 363 > 319 3.65 105  10 9.2 89  10 11.7 0.05
363 > 169 tions of PFCAs were very low, with PFOA having the highest
PFOA 413 > 369 3.84 87  7 8.3 102  8 7.7 0.05 concentrations (1.28 ng/L).
413 > 169 The wafer photolithographic process in the SEM-A is known to
PFNA 463 > 419 4.11 88  13 14.7 103  8 7.8 0.10 be the critical user of PFCs (especially PFOS-related substances)
463 > 219
(Brooke et al., 2004). PFOS-related substances form photoresists,
PFDA 513 > 469 4.43 93  10 10.2 90  13 14.2 0.05
513 > 269 serve as an antireflective thin coating, and can be used as surfac-
PFUnA 563 > 519 4.80 71  10 13.6 77  2 10.6 0.25 tants in the developer solution in the photolithographic process
563 > 269 (Brooke et al., 2004). Approximately 200 tons of wastewater are
PFDoA 613 > 569 5.18 53  6 11.9 61  8 12.6 0.25
generated each day from this process. We were, therefore, unsur-
613 > 269
prised when analysis revealed all of the targeted PFASs (PFOS-related
 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372 1369

Table 3 was indeed the main contributor of PFCs (especially PFASs) to final
Perfluorinated chemicals (PFCs) concentrations determined in a semiconductor waste effluents in this semiconductor fabrication plant. The corre-
fabrication plant (SEM-A) waters (pure water, wafer photolithographic wastewater,
and final effluent).
sponding masses of PFBS, PFHxS, and PFOS generated each day
from SEM-A manufacturing processes were then estimated to be
Compounds Pure water Photolithographic Final effluent >0.38 kg, >0.68 kg, and >0.67 kg, respectively. Consumption of
(ng/L) wastewater (ng/L) (ng/L)
PFOS-related substances in semiconductor applications in the
PFBS 5.7 5,153,330 75,430
European Union (EU) for 2002 was estimated to be 470 kg/year
PFHxS 24.2 9,930,000 133,330
PFOS 36.7 12,566,670 128,670 (Brooke et al., 2004), and this number remained approximately
PFHxA nd na 76.4 constant for the following years. The PFC levels we have identified
PFHpA 0.1 na 8.8 in wastewater from one Taiwanese semiconductor fabrication plant
PFOA 1.4 na 118.3 alone have already exceeded the EU’s total usage. Moreover, in
PFNA nd na 7.7
PFDA 0.2 na 7.5
addition to the single plant studied here, Taiwan has 12 other
PFUnA nd na 9.1 semiconductor firms, which operate a total of 47 fabrication plants.
PFDoA 0.2 na 2.9 Taken together, the PFC substances generated from Taiwanese
na, Not available; nd, Not detected. semiconductor fabrication plants could be substantial and certainly
warrant further investigation into their potentially serious risks to
ecological and human health.
substances) in the plant’s wastewater effluents at extremely high
concentrations, the highest being PFOS (12.566 mg/L), followed by
PFHxS (9.930 mg/L) and PFBS (5.153 mg/L). Because of the high 3.3. PFC concentrations in an electronic/optoelectronic plant (ELE/
PFAS levels, direct injection of water samples into LC–MS/MS OPTO-A) wastewater
was performed. PFCAs were not detected, indicating that their
concentrations in residuals from the photolithographic process PFC levels were determined in 18 raw waste effluents from an
were <1 mg/L. The only other semiconductor wastewater study to electronics/optoelectronics fabrication plant (ELE/OPTO-A). Fig. 2
date (Tang et al., 2006) demonstrated even higher PFOS concen- shows the percent distribution of PFCs (scaled up to 100%) in each
trations (1650 mg/L) from the semiconductor fabrication’s photo- sample. Analysis revealed a different PFC distribution in effluents
lithographic process, although daily flow data were not reported. from raw waste versus effluents from SEM-A. Among the PFCs
Waste streams from the photolithographic section combine detected, PFOA, PFOS, and PFDA were the most prevalent constit-
with waste streams from other processes to make up the final uents, respectively, contributing an average of 72, 16, and 9% to each
waste effluents, which are estimated to be >5000 tons/day. The effluent sample. PFOA and PFOS were also the most frequently
final waste effluents were treated only to minimal effluent stan- detected PFCs and were present in all samples, at concentrations
dards (temperature 35  C, BOD 300 mg/L, COD 500 mg/L, S.S. ranging from 1.6 to 46.2 mg/L (PFOA) and 1.0 to 51.4 mg/L (PFOS).
300 mg/L, and concentrations of regulated metals (Hsinchu Science PFDA (a possible precursor of PFOA) was detected in 17 out of the 18
Park, 2003)) before being discharged into the receiving rivers. In samples, with detected concentrations <11.3 mg/L. PFHxS, PFUnA,
samples from these end-stage effluents, PFASs were again present and PFDoA were only detected in four samples, all at <2 mg/L. On
at the highest concentrations, ranging from 0.075 to 0.133 mg/L, a more macroscopic scale, it is worth noting that the electronic/
while PFCAs were all in the ng/L range (the highest being PFOA, at optoelectronic plant we surveyed generates about 335 tons of
118 ng/L). This finding indicates that the photolithographic process waste effluent each day, corresponding to the release of nearly 15.5,

PFHxS PFDA PFOS PFUnA PFOA PFDoA

100

90

80

70
Perercentage of PFCs

60

50

40

30

20

10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Fig. 2. Percent distribution of perfluorinated chemicals (scaled up to 100%) in each of the 18 raw waste effluents from an electronics/optoelectronics fabrication plant (ELE/OPTO-A).
1370 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372

17.2, and 4.6 g/day of PFOA, PFOS, and PFDA to downstream (PFOS, PFOA, and PFDA) identified in upstream ELE/OPTO-A
water bodies. wastewaters contributed almost half of the river’s PFC load.

3.5. Comparison of PFOS, PFOA, and PFDA concentrations in three of

3.4. Occurrence of PFCs in the receiving river waters
Taiwanese rivers vs. other countries
Fig. 1 is a map of the sampling area, which includes three major
Besides effluents from the semiconductor, electronics, and
sources of potential PFC contamination: Hsinchu Science Park
optoelectronic industries, waste discharges from existing munici-
(HSP), ELE/OPTO-A, and a small optoelectronics factory. HSP was
palities and continuing urbanization may impact the concentration
established in 1980, and by the end of 2004, a total of 384 high-tech
profile of PFCs in the aqueous environment. We have shown here
companies had been established with a primary focus on semi-
that PFOS, PFOA, and PFDA are the predominant PFCs occurring in
conductor research and production (Hsinchu-Science-Park, 2008).
Taiwan. Table 4 compares our observed concentrations of these
SEM-A is one of the 27 semiconductor fabrication plants located
three compounds to levels from similar river studies performed
inside the HSP. Waste effluents from SEM-A, which combine with
elsewhere in the world. Note that samples from the Keya River,
waste from the other semiconductor and optoelectronic factories in
which is greatly impacted by upstream wastewaters from HSP,
the HSP, add up to approximately 105,000 tons/day and are
display PFOS concentrations (5440 ng/L) which are significantly
released together to the receiving Keya River. The Touchien and
higher than levels reported for other rivers (Table 4).
Xiaoli rivers are the respective receiving river bodies for ELE/OPTO-
In the case of PFOA, our results are within the range of previ-
A and another small optoelectronic plant.
ously reported values. As predicted, higher PFOA levels were seen
Fig. 3a plots the logarithmic concentrations of the PFCs found in
in rivers impacted by industrial discharges, while smaller amounts
the Keya, Touchien and Xiaoli rivers; as shown, PFOS, PFOA, and
were detected in rivers affected by municipal or urban wastewater
PFDA were again the most prevalent PFCs in all river samples, with
discharges. The rivers Tánaro and Po in northern Italy had the
PFOS detected at the highest concentrations (45–5440 ng/L). PFCs
highest reported PFOA values (between 337 and 1270 ng/L), prob-
were more frequently detected and were present at relatively
ably due to the presence of a nearby fluoropolymer manufacturer.
higher concentrations in the Keya River, with eight out of ten tar-
The Tennessee River in the southern United States, on whose banks
geted PFCs detected. In contrast, the Xiaoli River was mostly free of
a fluorochemical manufacturing facility is located, was the second
PFCs, and only trace amounts of PFOS (82 ng/L), PFOA (17 ng/L),
most polluted, with PFOA levels similar to those of the Keya River
PFNA (6 ng/L), and PFDA (11 ng/L) were identified. Fig. 3b demon-
(310 ng/L), which itself is heavily impacted by semiconductor
strates the percent distribution (scaling up to 100%) of PFCs in each
manufacturing wastewaters from the HSP. PFOA concentrations in
river. PFC distribution in rivers was shown to be greatly impacted
Taiwanese rivers were higher than in Japan’s Tsurumi River (few
by upstream industrial sources, which may be explained by the
ng/L), China’s Pearl River, and several rivers in Germany, whose
persistent bioaccumulation of many PFCs (especially PFOS and
sources may be municipal or urban wastewaters. For Taiwanese
PFOA) in the environment. This was affirmed by high PFAS contri-
rivers, size and flow had only negligible influence on PFOA and
butions seen in SEM-A effluents (Table 3) and correspondingly high
PFOS concentrations when compared to other rivers; thus the
PFAS concentrations and percentages (>95% among all PFCs) in the
sources identified upstream were most likely to be the major cause
Keya River, which is directly downstream of SEM-A and thus the
of the observed PFC levels. Our PFDA data showed that concen-
HSP itself. Similarly, in the Touchien River, major constituents
trations in the rivers sampled here were higher than in other rivers
worldwide, highlighting the greater impact of PFDA on Taiwanese
a 10000
rivers. This may be due to semiconductor and photonic industrial
wastewater discharges wherein higher concentrations of PFDA
Concentration (ng/L)

1000
PFBS were also found.
PFHxS Overall, when concentrations of the three primary PFCs are
PFOS summed and compared with total PFC levels in rivers worldwide,
P
100 PFHxA the Keya River leads the pack ( PFC ¼ 5765 ng/L), with levels
PFHpA which should raise alarms for the potential effects on ecological and
PFOA human health. Furthermore, the Touchien and Xiaoli rivers dis-
10 P
PFNA played much lower total PFC concentrations ( PFC ¼ 110  8 ng/L),
PFDA in the same range as China’s Pearl River (115 ng/L) and Japan’s Uji
1
PFDoA River (120 ng/L). The comparison in Table 4 clearly demonstrates
Keya River Touchien River Xiaoli River that the semiconductor/electronics industry dominated all other
possible sources of PFC introduction into the aqueous environment
b 100 and depicts the overall impact of that industry’s activities on local
90 and downstream waters.
80
70 3.6. Risk of these compounds in the river waters
60
50 Humans can be exposed to PFCs by consumption of river water
40 through public water distribution. A water treatment plant is sit-
30 uated downstream of the Touchien River which converts river
20 water into drinking water for a nearby population (Fig. 1 shows the
10 three intake locations). Previous studies have shown that existing
0 drinking water treatment processes do not efficiently remove PFCs,
Keya River Touchien River Xiaoli River and consequently, significant levels can be identified in drinking
Fig. 3. (a) The logarithmic concentrations of the perfluorinated chemicals (PFCs)
water (Skutlarek et al., 2006). Population exposure by this route
detected in the Keya, Touchien, and Xiaoli rivers; (b) percent distribution (scaling up to may represent a considerable health risk. Acceptable threshold
100%) of PFCs in each of the three rivers. values for PFOA and PFOS in drinking water have been fixed at
 A.Y.-C. Lin et al. / Environmental Pollution 157 (2009) 1365–1372 1371

Table 4
PFOA, PFOS, and PFDA concentrations detected in Taiwanese River waters and compared with previous studies around the globe.

Region Occurrence area Impact PFOA (ng/L) PFOS (ng/L) PFDA (ng/L) Ref.
Taiwan Xiaoli I 17.3 82 11.3 Present study
Taiwan Touchien I 10.9 48.9 58.2 Present study
Taiwan Keya I 310 5440 14.6 Present study
Japan Tsurumi River STP 13.4–15.9 179.6–179.9 2.1–3.9 Zushi et al. (2008)
Japan Uji River I, P 100–110 8.7–10 – Senthilkumar et al. (2007)
China Yangtze River I, U, P 2.0–260 <0.01–14 <0.01–3.8 So et al. (2007)
China Pearl River Guangzhou I, U, P 0.85–13 0.9–99 <0.13–0.57 So et al. (2007)
Germany Rivers WWTP 1.0–14 0.7–15 Becker et al. (2008)
N-Italy Po River I 337 <0.1–25 – Loos et al. (2008)
Tánaro River 1270 2 –
U.S.A Tannessee River Highest by fluorochemical nd-598 16.8–144 – Hansen et al. (2002)
manufacturing facility

I, industrial discharge; STP, sewage treatment plants; U, urban discharge; WWTP, wastewater plant; P, populated area.

0.5 mg/L and 0.3 mg/L, respectively, by the Minnesota Department of
Health (2007), while a value of 0.04 mg/L is accepted by the State of
New Jersey as a non-carcinogenic level for PFOA. We have found
that levels of these compounds in the Keya River exceed the
accepted safe thresholds. Assuming no PFC removal by drinking
water treatment plants (a real possibility, as shown by Skutlarek
et al. (2006)), it is clear that consumption of water from the Keya,
Touchien, and Xiaoli rivers carries significant risk. Furthermore,
a study of structure–activity relationships by Kleszczynski et al.
(2007) revealed that toxicity increases with increasing length of the
original fluorocarbon chain, implying that PFDA, which was
detected in all three rivers studied here, may exhibit increased
toxicity compared with PFOA.
4. Conclusions
Concentrations of three (C4–C8) perfluoroalkyl sulfonates
(PFASs) and seven (C6–C12) perfluoroalkyl carboxylates (PFCAs)
were determined in semiconductor, electronic, and optoelectronic
industrial wastewaters and in their receiving river bodies. Our
results suggest that these manufacturing facilities, located directly
upstream of our sampling spots, are the primary causes of PFC
contamination in the Keya, Touchien, and Xiaoli rivers. The Keya
River in particular was found to be polluted with PFCs derived from
effluents out of Hsinchu Science Park (HSP). A plausible risk to
human and aquatic life exists, as demonstrated directly by the
quantity of PFCs detected in these rivers and indirectly by the many
drinking water intake sites situated downstream of our sampling
points. The results presented here warrant future study of the fate
of PFCs in drinking water treatment plants, as well as of current and
future health risks of continued PFC exposure.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.envpol.2008.11.033.
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