water research 43 (2009) 23992408

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Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid

(PFOA) in sewage treatment plants

Jing Yua, Jiangyong Hua,*, Shuhei Tanakab, Shigeo Fujiib

a
Division of Environmental Science and Engineering, National University of Singapore, 10 Kent Ridge Cresent, Singapore 119260, Singapore
b
Research Center for Environmental Quality Management, Kyoto University, Yumihama 1-2, Otsu, Shiga 520-0811, Japan

article info abstract

Article history:
Received 15 October 2008
Received in revised form
20 February 2009
Accepted 1 March 2009
Published online 18 March 2009
Keywords:
PFOS
PFOA
Conventional activated
treatment (CAS)
Membrane biological reactor (MBR)
Sludge retention time (SRT)
Seasonal variation
In this study, the concentrations of PFOS and PFOA in the biological units of various full-
scale municipal sewage treatment plants were measured. Samples of influent, primary
effluent, aeration tank effluent, final effluent and grab samples of primary, activated,
secondary and anaerobically digested sludge were collected by 5 sampling events over one
year. The two sewage treatment plants (STPs) selected for this study include plant A
receiving 95% domestic wastewater and plant B receiving 60% industrial wastewater and
40% domestic wastewater. PFOS and PFOA were observed at higher concentration in
aqueous and sludge samples in plant B than that of plant A. Mass flow of PFOS increased
significantly (mean 94.6%) in conventional activated sludge process (CAS) of plant B, while
it remained consistent after the secondary treatment in plant A. Mass flow of PFOA
sludge increased 41.6% (mean) in CAS of plants A and B and 76.6% in membrane biological reactor
(MBR), while it remained unchanged after the treatment of liquid treatment module (LTM).
Our results suggest that mass flow of these two compounds remains consistent after
treatment of activated sludge process operating at short sludge retention time (SRT).
Seasonal variations of PFOS in concentrations of raw sewage were found in plant A, while
PFOA did not have significant seasonal variation in both plants A and B.
2009 Elsevier Ltd. All rights reserved.

1. Introduction two PFCs, perfluorooctane sulfonate (PFOS, C8F17SO3) and per-

Effluent from wastewater treatment plants is one of the impor-
tant routes for the introduction of certain organic contaminants
into aquatic ecosystems. Several studies have described efflu-
ents of sewage treatment plants (STPs) as an important source
for metals, chlorinated organic compounds to aquatic environ-
ments (Irvine et al., 1993; Loganathan et al., 1997). Perfluorinated
compounds (PFCs), a class of emerging environmental pollut-
ants, have been widely used for the last 50 years in industrial and
commercial applications, such as coatings, shampoos, electro-
plating, fire-fighting foams, stain repellants for furniture and
carpets. Widespread usage of these compounds has been
attributed to their contamination in wastewaters. Occurrence of
fluorooctanoic acid (PFOA, C7F15COO) has been reported in STPs
(Kissa, 2001). Various contamination levels were observed in the
influent and effluent of municipal STPs in Iowa City (Boulanger
et al., 2005), in Kentucky and Georgia, respectively (Loganathan
et al., 2007), in 10 national wide municipal STPs in U.S.A
(Schultz et al., 2006a) and in the effluent of 6 U.S.A cities (Sinclair
and Kannan, 2006). The discharge of municipal wastewater
effluent is therefore one of the major routes for introducing PFOS
and PFOA that are used in domestic, commercial and industrial
settings into aquatic environment. Recently, there has been
increasing concern about the fate and behavior of PFOS and
PFOA in sewage treatment plant due to their biotic and abiotic
persistence and chronic toxicity (Prevedouros et al., 2006; Hof

* Corresponding author. Tel.: 65 65 164 540; fax: 65 67 744 202.

E-mail address: esehujy@nus.edu.sg (J. Hu).
0043-1354/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2009.03.009
2400 water research 43 (2009) 23992408

et al., 2004; 3M, 2003). Sinclair and Kannan (2006) observed that
mass flow of PFOS and PFOA in aqueous phase increased
significantly after secondary treatment in a sewage treatment
plant with industrial influence, while no increase in mass flow of
PFOA was found in another sewage treatment plant with no
industrial influence. Furthermore, Schultz et al. (2006b) identi-
fied the fate and behavior of these two compounds in both
aqueous phase and solid phase (sludge) during each step of
municipal wastewater treatment plant. It was observed that
mass flow of PFOS or PFOA either increased or remained
consistent, indicating conventional activated sludge process
cannot effectively remove these compounds. However, limited
data are available on the concentration levels of PFCs in various
full-scale activated sludge treatment processes, such as
membrane biological reactor (MBR).
The objective of this study was to determine the concentra-
tion levels of PFOS and PFOA in full-scale conventional activated
sludge processes and membrane biological reactor, as well as in
an activated sludge process operated with a short SRT. This
study investigated the effect of SRT on levels of these two
compounds in the activated sludge process. Furthermore,
seasonal variation in the concentrations of PFOS and PFOA in
sewage treatment plant was studied. In order to achieve these,
aqueous and solid samples were taken from each treatment unit
of STPs, A and B.
2. Materials and methods
2.1. Sampling events
Samples were collected from two STPs, plant A and B in
Singapore. Plant A, the largest STP in Singapore, serves
a population of approximately 1,700,000 people. It treats
361 MLD (million litre per day), which consists of 95%
domestic wastewater and 5% industrial and commercial
wastewater. The plant comprises of conventional activated
sludge process lines (CAS1) in parallel with liquid treatment
module (LTM) and MBR (Fig. 1). CAS1 is operated with an SRT
of w15 days and hydraulic retention time (HRT) of 8 h, while
LTM with SRT of w3.5 days and HRT of 6 h. For the MBR, SRT
and HRT are w20 days and 6 h. The MBR consists of a sus-
pended growth biological reactor combined with a submerged
microfiltration membrane module. Plant B, which only has
conventional activated sludge process (CAS2), treats 205 MLD,
among which 60% is industrial wastewater and 40% is
domestic wastewater. It serves a population of approximately
980,000 people and is operated with an SRT of w12 days and
HRT of 10 h. Both CAS1 and CAS2 have similar treatment
process, mainly consisting of primary clarifier (PC), aeration
tank (AT) and secondary clarifier (SC). The produced sludge
together with the solids obtained from the primary clarifier is
disposed by thickening centrifuges, followed by anaerobic
digester and dewatering centrifuges.
Sampling events were conducted in the October 2006,
December 2006, March 2007, September 2007 and December
2007 in plants A and B. December is the wet season, which has
much more precipitations than other months. Other sampling
events occurred during dry season. For the sampling in
December, it was performed after it had been raining for
a week and when it was raining. For the sampling in other
months, there was no significant rainfall in the period. During
the sampling events, outside temperature ranged from 21  C
to 32  C. Due to lack of auto samplers, grab aqueous samples,
instead of 24-h composite samples, were taken in plants A and
B. Usually 24-h composite sampling is conducted to identify

Grit Primary Aeration Secondary

Screen 267 MLD
Raw Removal (205 MLD)* Clarifier Tank Clarifier
Effluent
Sewage
Influent Primary Aeration Secondary
effluent effluent effluent
Inorganic Primary
Solids Sludge Returned Secondary
Activated Sludge Sludge
CAS 1 (CAS2 Thickening Anaerobic
in Plant B) Centrifuge Digester

Dewatering
Thickened Centrifuge
sludge Dewatered
Returned Digestered Sludge
Liquid sludge
Primary Liquid Treatment Seconday
Clarifier Module Clarifier
71 MLD
LTM Effluent
LTM-in LTM-pc LTM-eff

Returned
Primary Activated Sludge
MBR MBR-sup
23 MLD Clarifier
MBR Effluent
MBR-pc MBR-eff
Grab sample

* denote the flowrate of CAS2 (plant B)

Fig. 1 Flow scheme of the sewage treatment plants A (CAS1, LTM and MBR) and B (CAS2). * Denotes the flow rate
of CAS2 (plant B)
 water research 43 (2009) 23992408
Table 1 LOD, LOQ and recovery of PFOS and PFOA in
wastewater and sludge.
Analyte Wastewater Sludge Recovery
LOD LOQ LOD LOQ wastewater sludge
(ng/L) (ng/L) (ng/g) (ng/g)
PFOS 0.1 0.25 1 2 91% 84%
PFOA 0.5 1 5 8 82% 70%
behavior and fate of those compounds in STPs accurately.
Sampling points were shown in Fig. 1. Grab samples of
primary, activated, secondary, returned activated, thickened
and anaerobically digested sludges were also collected.
2.2. Sample preparation and extraction
All wastewater and sludge samples were collected and stored
in high-density polyethylene bottles. Sample bottles were
kept on ice and brought back to the laboratory within 4 h of
collection. Immediately, all aqueous samples were prepared
by centrifugation at 3000 rpm for 10 min followed by filtration
by GFF (glass filter filter) (0.45 mm, Whatman, U.S.A) and stored
at 20  C until extraction. Particulate matter (suspended
solids) was separated from the raw influent by centrifugation.
Sludge samples were centrifuged at 5000 rpm for 15 min to
remove supernatant and proceeded to freeze dryer (Alpha 1-2
LDplus, Christ, U.S.A). Dry sludge was ground and homoge-
nized with a mortar and pestle.
Teflon bottles, Teflon-lined caps, and any suspected fluo-
ropolymer materials were avoided throughout the analysis. In
most cases, samples were extracted within 24 h after collec-
tion; otherwise, samples were kept frozen until analysis.
Extraction procedure used was similar to that described
elsewhere (So et al., 2004) with modifications. Briefly, 0.5 L
filtrated water samples were extracted using 500-mg hydro-
philiclipophilic balance (500 mg, 6 cc HLB) cartridges (Waters,
U.S.A) according to the above method. Then an additional
solid phase cartridge, Sep-Pak plus silica cartridge (1 g,
Waters) was applied to further remove the interfering matrix
in the extracts of HLB cartridge. The HLB extracts in 4 ml
methanol were diluted with 6 mL dichloromethane. The silica
cartridge was preconditioned with 5 mL dichloromethane/
methanol (60:40, v/v). Then the diluted extracts were loaded
onto the silica cartridge and collected into a polypropylene
tube. The extract was evaporated to dryness under a gentle
nitrogen stream and reconstituted in 0.5 mL methanol/
aqueous ammonium hydroxide (0.01%) solution (70:30, v/v).
Sludge samples were extracted according to an established
method (Higgins et al., 2005) and further cleaned by silica
cleanup method. Briefly, 100 mg freeze dried sludge was
transferred to a 50 mL polypropylene vial and extracted
according to the above method. Then the resulting extracts of
35.1 mL were loaded onto Oasis HLB cartridge (500 mg) at
2 mL/min, which was preconditioned by 5 mL of methanol
and 10 mL of 1% acetic acid. Subsequently the cartridge was
eluted by 2  2 mL methanol after it was rinsed by 10 mL Mill-
Q water. Instead of reducing matrix interference by dilution,
the silica cartridge was used to remove the matrix effect. The
2401
extracts were diluted with 6 mL dichloromethane. The diluted
extracts were loaded onto the silica cartridge after it was
preconditioned with 5 mL dichloromethane/methanol (60:40,
v/v). The eluent was concentrated under nitrogen to complete
dryness. The final extracts were kept to 1 mL by 70:30 (v/v)
methanol/aqueous ammonium hydroxide (0.01%) solution.
The extracts of both wastewater and sludge samples were
filtered by 0.2 mm nylon syringe filter to remove fine particles
and then stored at 20  C until analysis. Immediately prior to
LC/MS/MS analysis, the 0.5 mL aliquot of extracts was trans-
ferred to an autosampler vial and 50 mL of 50 mg/L aqueous
internal standard mixture containing perfluoro(2-ethox-
yethane)sulfonic acid (PFEES) and perfluorododecanoic acid
(PFDoA) was added.
2.3. Instrumental analysis
High performance liquid chromatograph, composed of an
HP100 liquid chromatograph (Agilent Technologies, U.S.A)
interfaced with a triple quadrupole MS/MS (Applied Bio-
systems, U.S.A) was applied to detect samples in the electro-
spray negative ionization mode. Separation of compounds
was performed on a 150  2.1 mm (5 mm) Zobax Extend C18
column (Agilent Technologies, U.S.A). A 10 mL aliquot of the
sample extract was injected into a guard column (XDB-C8,
2.1 mmi.d.  12.5 mm, 5 mm; Agilent Technologies, U.S.A)
connected sequentially to Zorbax Extend C18 column with
2 mM ammonium acetate aqueous solution (solvent A) and
methanol (solvent B) as mobile phases, starting at 3% B. The
flow rate was set at 300 uL/min. The gradient was held until
0.50 min, increased to 95% B until 6.00 min, held until
8.50 min, revert to original conditions at 8.51 min and was
held 3% B until 12 min. The column temperature was held
constant at 30  C.
The limit of detection (LOD), defined as the concentra-
tion that yielded an S/N ratio of higher than or equal to 3,
and the limit of quantification (LOQ), defined as the
concentration that yielded an S/N ratio of higher than or
equal to 10, were determined by the SPE extraction of
spiked Mill-Q water samples. The limit of quantification for
PFOS and PFOA was 0.1 ng/L and 0.5 ng/L in aqueous
sample, 1 ng/g dw (dry weight) and 5 ng/g dw in sludge
sample (Table 1). During the analysis of samples, proce-
dural blanks for PFOS and PFOA were less than the LOD,
indicating no contamination occurs in sampling and anal-
ysis. Each aqueous and sludge samples were analyzed and
injected into LC/MS/MS in duplicate in this study. Thus
average concentration of them comes from four observa-
tions (two replicate injections of two replicate samples).
Mean recovery of PFOS and PFOA was 91% (PFOS) and 82%
(PFOA) for aqueous sample and 84% (PFOS) and 70% (PFOA)
for sludge sample.
3. Results and discussion
3.1. PFOS/PFOA in wastewater
Sampling strategy can affect the concentrations of the ana-
lytes measured in sewage treatment plants. The 24-h
 2402
Table 2 Concentrations of PFOS/PFOA in wastewater and sludge from CAS1 and CAS2.
Date Sample Analyte Influent Primary effluent Aeration Secondary effluent Influent (particulate) Primary Activated Secondary Thickened Digested
site (ng/L) (ng/L) tank (ng/L) (ng/g dw) sludge sludge sludge sludge sludge
effluent (ng/g dw) (ng/g dw) (ng/g dw) (ng/g dw) (ng/g dw)
(ng/L)

Oct CAS1 PFOS 13.9  2.3 15.8  3.8 24.9  2.9 12.6  1.6 7.3  0.7 22.5  4.7 33.2  6.1 28.5  9.4 28.2  5.9 39.2  7.4

water research 43 (2009) 23992408

06 PFOA 16.3  3.9 11.1  1.84 25.9  4.6 24.3  2.9 <5 8.0  2.7 12.3  3.7 10.5  2.4 17.5  4.2 36.7  13.0
CAS2 PFOS 194.3  50.3 214.8  45.4 375.9  67.6 323.5  38.1 62.8  8.1 213.5  40.2 358.8  109.2 228.8  48.2 310.3  100.9 515.1  126.6
PFOA 56.5  16.1 41.2  8.6 88.6  22.5 77.4  13.7 6.1  0.8 17.9  6.4 24.9  7.1 28.8  1.4 36.6  9.4 69.0  12.2

Dec CAS1 PFOS 7.9  1.9 9.9  2.4 12.5  2.2 7.3  2.2 2.9  0.6 13.1  4.3 21.5  4.4 14.0  3.7 33.3  6.8 30.7  6.8
06 PFOA 14.1  4.0 12.1  2.8 22.6  5.5 15.8  2.8 <5 <5 8.3  2.2 6.5  1.3 21  5.2 17.4  5.4
CAS2 PFOS 56.3  8.3 48.1  8.1 90.7  16.3 95.6  11.4 31.4  5.4 145.1  26.1 245.1  36.1 162.5  30.1 291.6  47.9 445.2  65.6
PFOA 31.8  8.8 36.6  5.4 69.5  14.7 78.2  17.6 5.9  0.6 18.9  3.4 25.0  3.7 35.0  8.7 28.0  4.6 46.9  8.4

Mar CAS1 PFOS 12.7  4.1 10.7  1.6 13.7  1.8 11.3  1.7 6.0  0.8 14.1  2.7 29.0  7.0 15.5  2.4 35.2  11.6 35.7  7.9
07 PFOA 24.7  8.8 18.6  5.0 66.3  16.8 35.5  4.2 <5 13.7  3.1 20.4  5.9 7.6  2.5 27.4  6.2 45.8  10.7
CAS2 PFOS 78.4  13.2 89.2  22.0 196.2  35.3 157.6  27.9 36.0  4.8 317.9  67.2 617.7  109.5 377.1  59.6 390.1  70.1 702.2  173.2
PFOA 192.0  44.4 150.7  25.4 285.6  74.7 230.2  40.9 29.0  5.9 26.9  7.7 54.4  14.0 45.0  6.4 39.9  6.5 47.5  12.2

Sep CAS1 PFOS 25.3  4.2 22.7  3.2 17.7  3.2 16.7  3.7
07 PFOA 82.0  19.4 71.3  25.3 104.1  15.6 138.7  17.4
CAS2 PFOS 374.5  61.6 338.2  57.0 560.9  67.1 461.7  82.0
PFOA 638.2  135.9 531.7  87.7 939.6  161.1 1057.1  205.8

Dec CAS1 PFOS 9.2  2.3 9.9  2.4 11.9  2.1 11.3  2.4
07 PFOA 22.6  6.7 23.8  5.0 37.1  9.6 40.7  10.5
CAS2 PFOS 130.3  21.7 101.9  14.6 220.6  37.2 151.3  27.8
PFOA 73.9  20.3 89.4  24.6 148.3  36.2 152.8  37.1

: Not available.
 water research 43 (2009) 23992408 2403

Table 3 Concentrations of PFOS and PFOA in wastewater and sludges from LTM in STP A.
Date Analyte LTM-in (ng/L) LTM-pc (ng/L) LTM-eff (ng/L) LTM sludge (ng/g dw)

Oct 06 PFOS 15.2  2.1 19.1  3.5 15.9  1.6 21.5  5.8
PFOA 20.5  5.7 29.1  6.1 17.2  2.1 13.1  3.9

Dec 06 PFOS 7.3  1.5 6.4  1.1 5.3  1.3 9.0  2.2
PFOA 13.4  3.4 15.3  3.9 17.0  3.5 6.0  1.2

Mar 07 PFOS 19.2  3.3 16.4  1.6 14.4  2.5 25.1  4.7
PFOA 19.4  4.1 25.4  6.1 21.8  2.6 9.3  2.8

composite sample is appropriate to represent average
concentrations over 24 h in the wastewater steams of STPs.
Grab samples collected in this study, which could have been
collected at high or low flow period, may increase the varia-
tion in concentrations. Therefore, care must be taken when
concentrations of PFOS and PFOA measured were compared.
The measured PFOS and PFOA concentrations in waste-
water and sludge samples from STPs A and B are shown in
Tables 24. PFOS and PFOA were detected in all wastewater
samples collected from STP A and B. PFOS was observed at 5.3
29.8 ng/L in STP A, which is comparable to those measured in
the effluent of 4 STPs receiving domestic and commercial
sewage (Sinclair and Kannan, 2006). However, much higher
concentration of PFOS (48.1560.9 ng/L) was detected in STP B
receiving 60% industrial wastewater. These measured PFOS
concentrations are also much higher than those in the influ-
ents and effluents of 10 STPs mainly receiving domestic and
commercial sewage in USA (Schultz et al., 2006a), but much
lower than those in the effluents of Decatur which receives
influent from fluorochemical manufacture or industry.
Nevertheless, the comparable concentration was observed in
a wastewater treatment plant in Cleveland (3M, 2001), which
has no known fluorochemical sources. It suggests that
industrial sewage can contain a large amount of PFOS in
comparison with domestic and commercial sewage even
though there is no known source of fluorochemical exposure.
PFOA was the predominant contaminant in STP A, which
was measured at 11.2138.7 ng/L. Slight lower and comparable
PFOA concentration was reported in the influents and efflu-
ents of 10 STPs in USA (Schultz et al., 2006a). However, Sinclair
and Kannan (2006) observed much higher concentration in 4
STPs receiving domestic and commercial sewage. This
suggests that commercial sewage could be a significant source
of PFOA, which includes a wide range of sources (hospitals,
shopping malls and so on) and provides more variable amount
of PFOA. In addition, the predominance of PFOA over other
perfluorinated compounds was observed in other STPs (Sin-
clair and Kannan, 2006; Loganathan et al., 2007). In STP B,
PFOA concentration was detected in the range of 31.8
1057.1 ng/L, which is much higher than those of STP A and
those in a sewage treatment plant with similarly 60% indus-
trial influent (Sinclair and Kannan, 2006). It suggests the effect
of industrial influent on PFOA concentration is dependent on
the composition of the sewage that enters the sewage treat-
ment plants. Moreover, in this study, higher variation in
concentrations of both PFOS and PFOA was observed in STP B
than those in STP A, indicating industrial influent can result in
high concentration variation.
3.2. Seasonal variation
In STP A, PFOS concentration in influent of dry season showed
statistically significant difference from the wet season
( p 0.003), while PFOA had no such significant difference
( p 0.157) (Fig. 2). It seems that PFOS concentrations notice-
ably decreased during wet season, while there was no
discernable decrease in PFOA concentrations in surface
waters. The presence of PFCs in rainfall indicates rainfall
significantly affects their concentrations in surface water.
PFOS has been observed at a low concentration (0.59 ng/L) in
the precipitation (Loewen et al., 2005), while significantly
higher PFOA concentrations were reported in rainwater. Kal-
lenborn et al. (2004) reported that PFOA was the predominant
PFCs measured in rainwater samples from Sweden and
Finland with the greatest concentrations (11 ng/L and 17 ng/L,
respectively). Scott et al. (2006) also reported relatively high
PFOA concentrations (<0.189 ng/L) in the rainwater samples
from U.S.A and Canada. Based on the limited data, it seems
that PFOS concentration in rainwater is lower than that of
PFOA, which leads to their different seasonal variations in
surface water. Furthermore, runoff could also be the potential
PFCs sources during rainy weather. Rainfall may pick up and

Table 4 Concentrations of PFOS and PFOA in wastewater and sludges from MBR in STP A.
Date Analyte MBR-pc (ng/L) MBR-sup (ng/L) MBR-eff (ng/L) MBR sludge (ng/g dw)

Mar 07 PFOS 11.9  2.0 10.7  3.1 11.4  1.1 22.1  4.2
PFOA 16.6  3.9 30.4  5.2 32.1  9.1 12.1  2.3

Sep 07 PFOS 20.3  4.8 23.3  3.3 18.5  5.3

PFOA 67.7  11.8 113.9  13.6 93.8  26.6

Dec 07 PFOS 7.9  1.7 10.6  1.9 9.3  2.4

PFOA 19.6  3.1 31.7  6.3 30.4  5.4

: Not available.
2404 water research 43 (2009) 23992408

a 35 b 120

PFOA Concentration (ng/L)

PFOS Concentration (ng/L)
Dry season Dry season
30 100
Wet
25 season
Wet 80
season
20
60
15
40
10

5 20

0 0
1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11

Fig. 2 Seasonal variations in influent concentrations of (a) PFOS and (b) PFOA in STP. 1: Oct 06 (CAS1), 2: Mar 07 (CAS1), 3:
Sep 07 (CAS1), 4: Mar 07 (MBR), 5: Sep 07 (MBR), 6: Oct 06 (LTM), 7: Mar 07 (LTM), 8: Dec 06 (CAS1), 9: Dec 06 (LTM), 10: Dec 07
(CAS1), 11: Dec 07 (MBR).

carry away PFCs pollutants (such as oil, fire-fighting foam)
when it moves over and through the ground, which leads to
the occurrence of nonpoint source pollution (NPS) of PFCs.
Zushi et al. (2008) observed that some PFCs concentrations in
a river did not decrease with the increase of river flow rate
during the rainy weather possibly due to the NPS of PFCs. As
a result, the decreased PFOS concentrations in surface water
may result in their decrease in wastewater correspondently
after surface water is treated by water treatment plants and
then subsequently utilized by various consumers. However, in
STP B no significant difference between dry season and wet
season for both PFOS ( p 0.52) and PFOA ( p 0.274) was
observed despite slight lower concentration was observed in
wet season (Fig. 3). It is likely that high concentration of
industrial influent overrides the effect of dilution by rain-
storm. In comparison, no large-magnitude seasonal variation
in concentrations of perfluorinated compounds was found
among spring, summer, fall and winter seasons in two
municipal sewage treatment plants (Loganathan et al., 2007).
3.3. Mass flows of PFCs in STPs
The average mass flow was calculated by multiplying average
PFOS and PFOA concentrations in aqueous and solid phase by
the daily flow of each treatment unit (Table 5). Total solid
waste is the daily mass of PFOS or PFOA associated with
primary sludge and waste activated sludge. Related informa-
tion on the wastewater and solid streams was obtained from
individual STPs. It is worthy to note that sampling strategy can
affect the concentrations of the analytes measured in sewage
treatment plants. Specially, grab sample, which could have
been collected at high or low flow period, may increase the
variation in concentration. As the concentration was based on
grab samples, it would result in additional variation in mass
flow besides the error of measurement. Therefore, only
change of more than 30% in mass flow would be taken into
consideration in this study (Loganathan et al., 2007).
CAS1, MBR and LTM, which are different treatment
processes, receive same raw sewage, while CAS2 receives
different raw sewage. No significant change in mass flow of
PFOS (24.5%16.0%) was observed in CAS1, MBR and LTM. It
is known that PFOS or PFOA cannot be biodegraded by acti-
vated sludge process (Lange, 2002). A reduction in mass flow
of PFOS or PFOA is neither expected nor observed (Schultz
et al., 2006b; Sinclair and Kannan, 2006) since biodegradation
of precursors such as fluorotelomer alcohols (FTOHs), per-
fluoroalkyl phosphates (PAPS), or fluorotelomer sulfonates
(FTSs) during activated sludge treatment process are likely
sources of increase of PFOS and PFOA. Specially, it is known
that 2-(N-ethyl perfluorooctanesulfonamido) ethanol (N-

a 500 b 900
PFOA Concentration (ng/L)
PFOS Concentration (ng/L)

450 Dry season 800 Dry season

400 Wet
Wet 700
season
350 season 600
300
500
250
400
200
150 300

100 200
50 100
0 0
Oct Mar Sep Dec Dec Oct Mar Sep Dec Dec
06 07 07 06 07 06 07 07 06 07

Fig. 3 Seasonal variations in influent concentrations of (a) PFOS and (b) PFOA in STP B.
Table 5 Mass flow (mg/d) of PFCs in influent, effluent and solid waste in CAS1, CAS2, LTM and MBR.
Site Date PFOS PFOA

Influent Influent Effluent Solid waste Mass Mass change Influent Influent Effluent Solid waste Mass Mass
(aqueous) (particulate) (total) change (%) (aqueous) (particulate) (aqueous) (total) change change (%)

CAS Oct 3722 487 3372 1014 177 4.2% 4355 ND 6496 292 2433 55.9%
1 06

water research 43 (2009) 23992408

Dec 3782 348 3540 534 57 1.4% 6782 ND 7565 403 1186 17.5%
06
Mar 3396 207 3009 607 13 0.4% 6584 ND 9465 501 3382 51.4%
07

MBR Mar 321 16 261 104 29 8.6% 451 ND 739 58 345 76.6%
07

LTM Oct 1076 130 1125 376 295 24.5% 1457 ND 1221 164 72 4.9%
06
Dec 1002 100 729 240 133 12.1% 1950 ND 2346 165 561 28.8%
06
Mar 1361 165 1022 260 244 16.0% 1378 ND 1544 180 346 25.1%
07

CAS Oct 39834 3862 66318 7870 30492 69.8% 11583 375 15867 800 4709 39.4%
2 06
Dec 20550 3395 34894 6200 17150 71.6% 11607 646 28543 1351 17641 144.0%
06
Mar 16072 2214 32308 12028 26050 142.5% 39360 1784 47191 1213 7260 17.6%
07

ND: not detectable; Mass change Influent (aqueous) Influent (particulate)  Effluent-Solid waste (total); Mass change (%) Mass change/[Influent (aqueous) Influent (particulate)].

2405
2406 water research 43 (2009) 23992408
Table 6 Calculated partition coefficient Kd in primary
sludge and activated sludge.
Compound Sludge type Kd (L/kg)
Range Mean (SD)
PFOS Primary sludge 8942237 1408 (481)
Activated sludge 7202324 1645 (511)
PFOA Primary sludge 188597 405 (149)
Activated sludge 201513 368 (106)
EtFOSE alcohol) and 2-(N-ethyl perfluorooctanesulfonamido)
acetic acid (N-EtFOSAA) can be biotransformed to PFOS
during activated sludge treatment (Boulanger et al., 2005;
Lange, 2000, 2002). Our result suggests that either raw sewage
of STP A do not introduce the precursors of PFOS or no
significant biotransformation occurs during these processes.
However, significant increase in mass flow of PFOS (mean
94.6%) was observed in CAS2, indicating biodegradation of
precursors may occur during the secondary treatment. As
CAS1 is running with the similar operational parameters (e.g.
SRT and HRT) compared to CAS2, the results suggest that
no precursors of PFOS be likely contained in the raw sewage
of STP A.
Mean mass flow of PFOA increased 41.6% (17.5%55.9%)
and 76.6% in CAS1 and MBR, respectively, while PFOA mass
flow remained unchanged after the treatment of LTM with an
SRT of 3.5 days. During activated sludge treatment some
precursors, especially 8:2 FTOH, have been shown to bio-
transform into PFOA (Dinglasan et al., 2004; Wang et al., 2005).
This suggests that no noticeable biodegradation of PFOA
precursors can occur in LTM though their presence in the raw
sewage has been demonstrated by mass increase in CAS1 and
MBR. Similarly, Clara et al. (2005) found that no biodegradation
of micropollutants, such as endocrine disruptors compounds
(EDCs) or pharmaceuticals could occur when the activated
sludge treatment system (CAS or MBR) was operated with an
SRT, which was lower than a critical SRT. Only at a higher SRT
which is more than the critical one, the microorganisms that
biodegrade certain micropollutants are able to be detained
and enriched in the system. It seems that the SRT of LTM is
lower than the critical one, resulting in no biodegradation of
precursors. Furthermore, mass flow of PFOA and PFOS
increased 17.6144.0% and 69.8%142.5% after the secondary
treatment of CAS2, respectively. It suggests that the precur-
sors of PFOS and PFOA be biodegraded at an SRT of w12 days,
which is higher than the critical SRT. Our results confirm that
change in mass flow of PFOS and PFOA may be determined by
both the presence of precursors and operating SRT of the
activated sludge system. SRT could thus be an important
operational parameter that affects the behavior pattern of
PFOS and PFOA.
PFOS and PFOA had no discernable mass change after the
treatment of primary clarifier in both STP A and B. In addition,
their mass flow in the inflow and outflow of primary clarifier
was equivalent at the 95% CI (confidential interval). It seems
primary clarifier has no noticeable effect on the mass flow of
PFOS and PFOA. Similarly, Schultz et al. (2006b) observed that
only 10% (PFOS) and 0.1% (PFOA) reduction in mass flow
occurred due to their sorption onto primary sludge.
3.4. PFOS/PFOA in sludge
PFOS and PFOA were detected in all sludge samples except for
one sample from STP A which was below LOQ of PFOA (Table
2). PFOS was observed at 13.146.0 ng/g dw in STP A, while 3.2
53.6 fold higher concentration (145.1702.2 ng/g dw) was
observed in STP B. Similarly, lower PFOA concentration (<5.0
44.2 ng/g dw) was observed in STP A, while higher PFOA
concentration (18.069.0 ng/g dw) in STP B was detected. In
comparison, Higgins et al. (2005) reported PFOS and PFOA
concentrations were in the range of 14.42610.0 and n.d
29.4 ng/g dw in the sludge samples of 8 STPs, respectively. In
addition, out results suggest that high concentration in
wastewater leads to high concentration in sludge which is due
to the partition between aqueous and solid phase. Neverthe-
less, due to its higher partition coefficient in comparison with
PFOA (Higgins and Luthy, 2006), PFOS was dominant in sludge
samples of both STPs A and B even though PFOA was domi-
nant in aqueous samples of STP A.
In terms of PFOS or PFOA concentration, there was no
noticeable difference among activated sludge samples
collected from LTM, MBR and CAS1. It seems their concentra-
tion in sludge is more relevant to the aqueous concentration
than sludge characteristics, which are affected by the sludge
retention time (Liao et al., 2001; Ng and Hermanowicz, 2005).
The partition coefficient Kd for primary sludge and acti-
vated sludge is estimated based on the data obtained by
dividing PFCs concentrations in primary sludge or secondary
sludge by their aqueous concentration in primary effluent or
secondary effluent (Table 6). Kd value of PFOS was in the range
of 8942237 L/kg (primary sludge) and 7202324 L/kg (activated
sludge), while significantly lower Kd value of PFOA was
observed at 188597 L/kg (primary sludge) and 201513 L/kg
(activated sludge), respectively. The mean Kd value of PFOS
was more than 3 times higher than that of PFOA, indicating
much more amount of PFOS adsorbed onto sludge as
compared to PFOA. High variations in Kd value for PFOS and
PFOA may be caused by different retention time of aqueous
and solid streams in primary and secondary clarifiers. In
addition, it seems that there is no significant difference
between Kd values in primary sludge and activated sludge.
Based on the data on organic carbon foc, calculated activated
sludge log Koc values (partition coefficient for the compound
onto a hypothetical pure organic carbon) were 2.983.49 for
PFOS and 2.432.83 for PFOA, respectively. In contrast, lower
organic carbon-normalized log Koc values were reported by
3M (2000) (2.573.1 for PFOS) and DuPont (2003) (1.92.17 for
PFOA) which were determined on sediments.
4. Conclusions
PFOS and PFOA were detected in all aqueous samples
collected from STP A and STP B, ranging from 5.3 to 560.9 ng/L
and 11.2 to 1057.1 ng/L, respectively. In sludge of STPs A and B,
PFOS and PFOA concentrations were in the range of 13.1
702.2 ng/g dw and <5.069.0 ng/g dw, respectively. Due to
industrial influence, PFOS and PFOA were observed at higher
concentration in aqueous and sludge samples in STP B than
that of STP A.
 water research 43 (2009) 23992408
Significant increase in mass flow of PFOS (mean 94.6%) was
observed in CAS2, while it remained consistent after
secondary treatment in CAS1. This is likely due to no occur-
rence of PFOS precursors in the raw sewage. Mean mass flow
of PFOA increased 41.6% in CAS1, 67.0% in CAS2 and 76.6% in
MBR, while it remained unchanged after the treatment of
LTM. Different behavior pattern of these two compounds was
found in LTM, an activated sludge process operated at very
short SRT. The findings suggest that change in mass flow of
PFOS and PFOA in secondary sludge treatment may be deter-
mined by the presence of precursors and operating SRT of the
activated sludge system.
Compared with STP A, higher concentrations of PFOS and
PFOA were detected in STP B receiving 60% industrial waste-
water. It suggests that industrial sewage contains a large
amount of PFOS and PFOA in comparison with domestic
sewage even though there was no known source of fluo-
rochemical exposure. Furthermore, industrial influent caused
high seasonal variation in concentrations of PFOS and PFOA.
Between dry and wet seasons, seasonal variation of PFOS was
observed in STP A, while PFOA had no significant difference in
both STP A and STP B. PFOS concentration in rainwater
observed by other studies was lower than that of PFOA, which
could lead to their different seasonal variations in surface
water. It is also likely that NPS of PFCs occurs in wet season,
which would contribute to consistent PFOA concentrations in
surface waters and subsequently result in indiscernible vari-
ation in PFOA concentrations in the wastewaters between dry
season and wet season.
Acknowledgement
The authors appreciate the financial support of JSPS-NUS fund
(R-288-000-033-112/123) and acknowledge the persons in STPs
who aided in sampling.
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