Survey of airborne polyfluorinated telomers in K eihan area, J apan Survey of airborne polyfluorinated telomers in K eihan area, J apan
Sayoko Oono,a,d Eriko Matsubara,a.d Kouji H. Harada,a Sokichi Takagi,b Sachiko
Hamada,c Akihiro Asakawa,a K ayoko Inoue,a Isao Watanabe,b Akio Koizumia,*
a Department of Health and Environmental Sciences, Kyoto University Graduate
School of Medicine, Kyoto 6068501, J apan.
b Osaka Prefectural Institute of Public Health, Osaka 5370025, J apan.
c Kyoto Prefectural Institute of Public Health and Environment, Kyoto 6128369, J apan.
d These authors contributed equally to this study
*Address correspondence to:
Akio Koizumi, M.D., Ph.D.
Department of Health and Environmental Sciences, Graduate School of Medicine,
Kyoto University, Yoshida Konoe, Sakyo, Kyoto 606-8501, J apan.
Tel: +81-75-753-4456, FAX: +81-75-753-4458,
Perfluorochemicals such as perfluorooctanoate (PFOA) are environmental
contaminants posing special public health concerns because of their long-term
persistence and bioaccumulation in the environment. They have been used widely
in surfactants, lubricants, firefighting foam and other applications (Kissa 2001).
PFOA and perfluorinated carboxylic acids (PFCAs) with various chain lengths
have been detected in a variety of environmental compartments. The sources of
PFCAs in the environment remain unclear, however degradation of fluorotelomers,
particularly fluorotelomer alcohols (FTOHs), might be indirect sources of PFCAs
(Ellis et al. 2004). Fluorotelomer alcohols are volatile and may undergo
long-range transport. FTOHs are currently produced and used as intermediates for
the synthesis of coatings, polymers, inks, adhesives, waxes and so on.
PFOA and related compounds have also been detected in the environment in
Japan (Nakayama et al. 2005). We have determined PFOA in surface water all
over Japan and have found intensive contamination of surface water by PFOA in
the Keihan (Osaka-Kyoto) area (Saito et al. 2004). In addition, serum levels of
PFOA in Kyoto residents were significantly higher than those in residents from
other areas of Japan (Harada et al. 2007; Harada et al. 2004). These data
collectively suggest area-specific sources of PFOA in the Keihan area. The
air-borne PFOA levels were found to be considerably higher at sampling sites on a
busy traffic route (Oyamazaki, Kyoto) than on an urban road (Harada et al. 2005;
Harada et al. 2006). In Kyoto, the estimated daily intake of PFOA from this route
was comparable to that from tap water.
The aim of the present study was to evaluate the concentrations of airborne
FTOHs in the Keihan area. This information may provide an insight into the
origin of PFOA in the environment.
MATERIALS AND METHODS
The test materials, 1H,1H,2H,2H-perfluorooctanol (6:2 FTOH; purity >98%),
1H,1H,2H,2H-perfluorodecanol (8:2 FTOH; >97%) and 1H,1H,2H,2H- perfluoro-
1-dodecanol (10:2 FTOH; >96%) were purchased from Alfa Aesar (Ward Hill,
MA). 1H,1H,2H,2H-perfluorodecyl acrylate (8:2 FTOAcryl; >96%), was
purchased from Lancaster Synthesis (Lancashire, UK). 1H,1H,2H,2H-
heptadecafluorodecyl methacrylate (8:2 FTOMethacryl; >98%) was from
Fluorochem (Derbyshire, UK).
heptadecafluoro-1-nonanol (8:1 FA; >98%) was purchased from Wako Pure
Chemicals (Osaka, Japan). 1D,1D,2D,2H,313C- perfluorodecanol was donated
by the Environmental Protection Agency of the U.S.A. (originally synthesized
by DuPont, Wilmington, DE).
Air samples were collected on quartz fiber filters (QF 8˝ x 10˝; QR-100, Sibata,
Tokyo, Japan) for particulate phase and glass columns (90 mm i.d.) with a
polyurethane foam (PUF 50 mm) followed by activated carbon fiber felts (ACF
10 mm; KF-1700F, Toyobo, Osaka, Japan) for the gaseous phase, using
high-volume air samplers (HV-700F, Sibata, Tokyo, Japan) at approximate flow
rates of 700 L min-1 for 24 hours, as previously reported (Takazawa 2006). ACF
and PUF slices were prepared by soaking in ethyl acetate, followed by drying
under vacuum. QF filters were rinsed several times with methanol and ethyl
acetate, and dried in a clean room. All sampling media were wrapped in
polyethylene bags for transport to the sampling site.
Air samples were collected at 5 sites in the Keihan area, Japan: Sakyo (SA:
Kyoto city, population 1,472,764), Morinomiya (MO: Osaka city, 2,636,680)
and 3 sites in Higashiyodogawa (HI1, HI2 and HI3: Osaka city) (Figure 1). Ten
samples were collected at Sakyo (October 2 to December 19). Four samples
were collected at Morinomiya (September 29 to December 19). Ten samples
were collected at Higashiyodogawa (October 16 to November 12). Field blanks
(ACF, PUF and QF) were sent to the sampling sites with each set of samples,
placed in the same sites for 24 hours, and returned with the environmental
For extraction of samples, the three sampling media were analyzed separately.
Each media was soaked for 10 min in 50 mL of ethyl acetate, and this was
repeated 3 more times (200 mL total). The aliquots were combined and dried
with sodium sulfate. Isotope-labeled 8:2 FTOH was added to all extracts to
determine recoveries. The extracts were rotoevaporated and reconstituted into
hexane. The solutes were then rotoevaporated again and the concentrates were
cleaned on a silica gel column (Presep®-C Silica Gel, Wako Pure Chemicals).
The FTOHs were eluted with 5 mL of 25% ethyl acetate in hexane and the
eluates were then evaporated to 1 mL under a gentle stream of high-purity
nitrogen. 8:1 FA was added as an internal standard just prior to the GC/MS
analysis to correct for volume differences.
Each extracted solution was analyzed by gas chromatography-mass
spectrometry (Agilent 6890GC/5973MSD) in electron impact ionization mode
(GC-EIMS) using single ion monitoring. Analytes were separated on an
HP-5MS column (30 m x 0.25 mm i.d. x 0.25 µm film thickness) with a helium
carrier gas. Pulsed splitless injections (2 µL) were performed at an initial
pressure of 30 psi for 1.5 min, with the injector set at 200 °C, and the split was
opened after 1.5 min. The initial oven temperature was 50 °C for 4 min, ramped
at 20 °C min-1 to 140 C°, and then at 40 °C min-1 to 240 °C, followed by a 1 min
hold. The ion source and quadrupole were 230 and 150 °C, respectively.
Quantification was performed using standard curve analysis and the internal
standard 8:1 FA.
RESULTS AND DISCUSSION
Instrumental detection limits (IDL) were defined as the mass of analyte
producing a peak with a signal-to-noise ratio of 3, and ranged from 1 pg (8:2
FTOAcryl and 8:2 FTOMethacryl) to 10 pg (6:2 FTOH). Method quantification
limits (MQL) were defined as the mean blank concentration producing a
quantifiable response +10 standard deviations with 10 repetitions, and ranged
from 3 pg m-3 (8:2 FTOAcryl and 8:2 FTOMethacryl) to 24 pg m-3 (8:2 FTOH)
for 1,008 m3 of sample (Table 1). Breakthrough experiments were conducted by
spiking 1,000 ng of analytes onto PUF slices (Table 1).
Table 1. Limit of detection and recovery of fluorotelomers.
Q ion: quantifier ion, Rsd: relative standard deviation
Q ion IDL
(m/z) (pg) (pg m-3) PUF
Recovery of breakthrough
rsd ACF rsd Total mean rsd
6 3 87 19
5 4 88 29
3 2 79 16
8 3 88 11
532 1 3 8 3 89 14 97 89 23
Figure 1. Geographic locations of the air sampling sites in Keihan area, Japan.
Reported concentrations were not corrected for blanks and recoveries. For
statistical analyses, data below the MDL and MQL were converted to half these
The field blank response was not significantly different from the clean sampling
media. Though there was occasionally a blank concentration of 8:2 FTOH and
10:2 FTOH associated with ACF and PUF, the response was always low enough
(<10 pg m-3).
FTOH air concentrations determined are presented in Table 2. All analytes could
be determined in the gaseous phase of air samples. 8:2 FTOH and 10:2 FTOH
were above the MDL in all samples, while 6:2 FTOH, 8:2 FTOAcryl and 8:2
FTOMethacryl were detectable in 75%, 79% and 50%, respectively, of samples.
Except for Higashiyodogawa, the highest concentrations of FTOHs were for 8:2
FTOH (median 447 pg m-3; range 48-1743 pg m-3) followed by 10:2 FTOH (56
pg m-3; <16-196 pg/m3) and 6:2 FTOH (22 pg m-3; <MDL-44 pg m-3). 8:2
FTOH represents 83% (range 61-89%) of the total FTOHs. In contrast, 8:2
FTOAcryl (median 865 pg m-3; range 9-2952 pg m-3) and 8:2 FTOH (median
1864 pg m-3; range 310-4585 pg m-3) were both major components in
Higashiyodogawa. Three airborne FTOHs (8:2 FTOH, 10:2 FTOH and 8:2
FTOAcryl) and ΣFTOH concentrations were significantly higher in the samples
from Higashiyodogawa than those from Sakyo (Steel-Dwass test: p<0.05),
indicating possible point as well as diffuse sources. 8:2 FTOAcryl
concentrations in Higashiyodogawa were also significantly higher than those in
Morinomiya (Steel-Dwass test: p<0.05). Between Morinomiya and Sakyo, 6:2
FTOH concentrations in Sakyo samples were significantly lower (Steel-Dwass
test: p<0.05). The average temperature of the ambient air did not influence the
levels of fluorotelomers (Kendall’s τ: p>0.05).
The proportions of the three fluorotelomer alcohols (6:2 FTOH, 8:2 FTOH and
10:2 FTOH) were 3.7±2.9%, 85±6.0% and 11±5.1% (mean±standard deviation),
respectively. These proportions did not differ between the three sampling sites
(Kruskal-Wallis’s test: p>0.05 for each FTOH). Correlations between analytes
are shown in Table 3. There were significant correlations between 8:2 FTOH,
10:2 FTOH and 8:2 FTOAcryl (Kendall’s τ: p<0.05 after Bonferroni correction
for each combination). These correlations suggest that these compounds might
have a common source in the environment.
FTOH concentrations determined in this study and reported by North American
and European researchers are presented in Table 4 (Berger et al. 2005; Jahnke et
al. 2007; Shoeib et al. 2007; Stock et al. 2004). Compared to data published for
North America and Europe, 8:2 FTOH levels are significantly higher in Keihan.
However, 6:2 FTOH levels in Europe are slightly higher than in Keihan and
North America. These different patterns of FTOHs might result from the
formulations for industrial applications, although the environmental fate of the
FTOHs is unclear.
Table 2. Airborne fluorotelomer concentrations (pg m-3) in Keihan area, Japan.
(°C) FTOH FTOH
23-Aug 28.4 <MDL 884
2-Oct 20.1 28 277
7-Oct 18.6 15 580
11-Oct 19.0 22 217
24-Oct 18.5 26 229
1-Nov 15.8 <14 151
23-Nov 11.9 <MDL 48
28-Nov 14.7 <MDL 314
5-Dec 5.6 <MDL 1743
19-Dec 5.3 21 1054
(GSD) (2.4) (2.9)
29-Sep 23.0 44 866
28-Nov 15.9 27 199
5-Dec 7.7 41 999
19-Dec 7.2 30 729
(GSD) (1.3) (2.1)
16-Oct 20.9 <MDL 2745
17-Oct 20.9 170 4585
18-Oct 21.7 83 1910
6-Nov 19.6 <MDL 1818
7-Nov 15.1 16 549
8-Nov 13.0 83 3071
9-Nov 17.0 124 3778
10-Nov 19.4 28 1030
11-Nov 15.6 22 512
12-Nov 10.8 19 310
(GSD) (3.8) (2.5)
Temp: average temperature of ambient air; GM: geometric mean; GSD: geometric
6:2 8:2 10:2
Table 3. Nonparametric correlation (Kendall’s τ) among airborne fluorotelomers.
8:2 FTOH 6:2 FTOH 0.25 0.093
10:2 FTOH 6:2 FTOH 0.34 0.021
10:2 FTOH 8:2 FTOH 0.67 <0.001a
8:2 Acryl 6:2 FTOH 0.20 0.182
8:2 Acryl 8:2 FTOH 0.54 <0.001a
8:2 Acryl 10:2 FTOH 0.43 0.004a
8:2Methacryl 6:2 FTOH -0.03 0.830
8:2Methacryl 8:2 FTOH 0.07 0.651
8:2Methacryl 10:2 FTOH 0.18 0.264
8:2Methacryl 8:2 Acryl 0.40 0.011
a) p<0.005 corresponding to p <0.05 after Bonferroni correction
SA & MO
Table 4. Comparison of FTOH concentrations (pg m-3) with literature data
Location 6:2 FTOH 8:2 FTOH 10:2 FTOH
Arctic Cruise 3
Toronto, Canada 9
North America, urban a 53
North America, rural a 14
Hazelrigg, England 81
Manchester, England 188
Hamburg, Germany 66
Waldhof, Germany 64
Each concentration was an arithmetic mean.
a) North American urban cities includes Reno, Griffin, Cleves and Toronto; rural
cities, Winnipeg, Long Point.
To the best of our knowledge, the study presented here provides the first
environmental survey of 8:2 FTOAcryl and 8:2 FTOMethacryl. The
fluorotelomer alcohol acrylate and
intermediates used in the manufacture of telomer-based polymers. These esters
could be rapidly degraded under aerobic conditions into fluorotelomer alcohols
and acids (Berger et al. 2005). Since 8:2 FTOAcryl was only present as a small
portion of FTOHs in the areas other than Higashiyodogawa, it was suggested
Shoeib et al. (2006)
Shoeib et al. (2006)
Stock et al. (2004)
Stock et al. (2004)
Berger et al. (2005)
Berger et al. (2005)
Jahnke et al. (2006)
Jahnke et al. (2006)
methacrylate are unpolymerized
that there might be a point source of the acrylate ester and that degradation of
the ester into 8:2 FTOH might progress rapidly.
The GM (GSD) of the airborne PFOA concentrations (pg m-3) was 262.8 (1.4)
for Oyamazaki, Kyoto (Figure 1) in 2001-2002 (Harada et al. 2005), which is
comparable to the 8:2 FTOH concentrations in Sakyo. FTOHs have an
atmospheric lifetime of approximately 10-20 days (Ellis et al. 2004). Therefore,
airborne PFOA in Oyamazaki seems to originate, in part, from fluorotelomer
This paper gives evidence suggesting that the level of airborne FTOHs is
considerably higher in the Keihan area than in other areas, suggesting a possible
point source. Further studies are necessary to investigate the contribution of
airborne FTOHs to PFCA contamination in the Keihan area, including that of
We are grateful to Drs. Andrew B. Lindstrom, Mark J. Strynar and Shoji
Nakayama (NERL, USEPA) for donating the isotope-labeled internal standard.
This study was mainly supported by Grants-in-Aid from the Ministry of Health,
Labor and Welfare of Japan (H15-Chemistry-004), the Japan Society for the
Promotion of Science (17-1910) and the River Fund of the Foundation of River
and Watershed Environment Management, Japan.
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