1. Sources and Environmental Level of Organofluoro Compounds
Regional alliances and Sharing Information
for joint research - partnership & cooperation between local government -
Takeshi NAKANO
(Hyogo Pref. Inst. of Env. Sci.)
(Osaka University)

2. Organofluoro Compounds
(PerFluoro Alkyl Sulfonates, PFASs)
(PerFluoro Carboxylic Acids, PFCAs)
CF3(CF2)nSO3H
CF3(CF2)nCOOH
PerFluoro Octyl Sulfonate, PFOS : C8
PerFluoro Octanoic Acid, PFOA : C8
extensive use of PFOS, PFOA for useful excellent property
extensive use of PFOS, PFOA for useful excellent property
PFOS： coating material, flame retardant, antireflective film
PFOA： Teflon, water repellent etc
- persistent (resistant to decomposition in environment)
- persistent (in environment) - carcinogenic, disorder of reproduction, developmental defect (suggested) - half-life: human serum 8y(PFOS),4y(PFOA)
PFOS： coating, flame retardant, antireflective film etc
PFOA： Teflon, water repellent etc
- persistent (in environment) - carcinogenic, disorder of reproduction, developmental defect (suggested) - half-life: human serum 8y(PFOS),4y(PFOA)

3. PFOS/PFOA level PFOS/PFOA pollution enlargement globally PFOS PFOA
Wild life ; white bear
PFOS(1.3～>4000ng/g)、PFOA(<2.0～8.6ng/g) (2004, Martin et al)
PFOA
Human serum PFOS(<1.3～164ng/ml)、PFOA(<3～256ng/ml) (2004, Kannan et al)
Biota PFOS（<1～3680ng/g） （2002, Kannan et al）
Environmental water and air

4. Kansai (Kyoto, Osaka, Kobe)
Level of PFCs in Japan
Kansai (Kyoto, Osaka, Kobe)
-high conc. PFOA in river water, drinking water, serum samples
Study on level, source of PFOS/PFOA related chemicals and precursor : not enough
May 22, 2007
Kobe newspaper
In 2007, 3 years ago, News paper reported
In Kansai area (central western part of Japan) such as Kyoto, Osaka, Kobe
High conc. of PFOA detected in river water, drinking water and serum samples
At that time,
Study on Env. level and source (such as manufacturing , using )
PFOS/PFOA related chemicals and precursor was not enough..
Limited data for PFC related chemicals was available 3 years ago.

5. 47 prefectures in Japan
66 Env Sci Inst. located in local government

6. Joint research to collaborate between 7 Env Sci Inst. in Kansai region
©2008　Google
4 prefectures , 3 cities
Joint research to collaborate
between 7 Env Sci Inst. in Kansai region

7. Osaka Bay
Source : Ministry of Land, Infrastructure and Transport

8. Osaka Bay Source : Ministry of Land, Infrastructure and Transport
Osaka Bay Database
Source : Ministry of Land, Infrastructure and Transport

9. quick, appropriate chemical management & control
Study on sources, environmental level, and treatment technology of organofluoro compounds
alternative, precursor, impurity of PFCs
NIES
- high sensitivity / accuracy method
- collecting & sharing information
emission source in Japan
- PFC manufacturing plant 　 comprehensive survey
local government
　 env. monitoring
- PFC using plant
　 comprehensive survey
alternative, precursor, impurity of PFOS
NIES
- developing　high sensitivity / accuracy analytical　method
- collecting & sharing information
To elucidate emission source in Japan
comprehensive nventory survey for PFC manufacturing plant and using PFC plant
data reduction
find industry sector which need countermeasure
- apply treatment technology (adsorption , destruction)
quick, appropriate chemical management & control
data reduction
find industry sector
NIES
- apply treatment technology
quick, appropriate chemical management & control

10. sharing information using mailing list Kantou
Study on sources, environmental level, and treatment technology of organofluoro compounds
Kansai
contaminations of PFOS and related PFCs in Lake Biwa water
pollution of organic PFCs in the area of Osaka Prefecture
Evaluation of occurrence of PFOS, PFOS and related compounds around the manufacturing facility
source & evaluation of transboundary pollution of fluorotelomer (FTs)
concentration level of PFCs in coastal seawater in Kobe
the PFCs level and the type of discharging industries
Trend analysis of fluorosurfactants pollution by the archived samples in environmental specimen bank
sharing information using mailing list
Kantou

11. Kickoff meeting of C type Joint research
Oct in NIES (29 Env. Inst.)

12. PFOS isomer specific analysis
joint research using web server and mailing list effectively
Collaboration study make it possible developing analytical method of PFCs for various media
only PFOS, PFOA analysed before
Intensity
Retention time
- providing all PFCs STD
- sharing tasks to develop
- sharing information
isomer-specific, PFOS,PFOA, related compounds, precursor, high sensitivity, high resolution
PFOS isomer specific analysis
Implementation of joint research using web server/mailing list
分析法を各機関が相補的に向上させ、PFOS、PFOA以外の様々な類縁物質が分析可能に
統一STDの配布
参加機関が分析法検討分担
情報共有
汚染起源推定、代替物質への移行状況の調査等が可能に
target : air, water, biota
source estimation, evaluation for PFCs alternative transition
PFCs in air

13. isomer-specific analysis of PFOS (2009, Yamamoto)
Evaluation of occurrence of PFOS, PFOS and related compounds around the manufacturing facility
n-PFOS
35m2-S
45m2-S
24m2-S
3m-S
4m-S
5m-S
55m2-S
1m-S
44m2-S
6m-S
Shared sample A
Shared sample B
isomer-specific analysis of PFOS (2009, Yamamoto)

14. source and evaluation of fluorotelomer compounds(FTs)
analytical method of PFCAs, PFASs, fluorotelomer (FTs)
High volume
air sampler QF
PUF
ACF × 2
source and evaluation of transboundary pollution of fluorotelomer (FTs) using back trajectory analysis
gas phase
PFCAs、PFASs、フッ素化テロマー類の同時分析法を検討
モニタリング調査を開始、バックトラジェクトリー解析を通して排出源特性や越境汚染の評価を行う
gas phase
particlulate

15. source and evaluation of fluorotelomer compounds(FTs)
FTs analysis in PFC product using HS-GC/MS
product before PFOA-compliant
product after PFOA-compliant

16. - mainline-branch line - effluent water
Summary
- mainline-branch line
- effluent water
finding new source of PFOS
流入幹線支線調査
・事業所排水調査
PFOSの汚染源となる業態を解明
20年度以降は濃度減少
POPs条約への追加に向けた削減活動
PFOS is on a declining trend
Reduction effort of PFOS

17. Effluent water from discharging industries
Survey of the PFCs level and the type of discharging industries (2009, Nishino)
　period:
Effluent water from discharging industries
airport
mainline
waste treatment plant

18. joint monitoring (water, air)
Summary
joint research above & beyond
joint monitoring (water, air)
排出源からの影響を多角的に把握
Osaka Bay：PFOA ↓ PFHｘA↑

19. PFOS, PFOA level（2009 May, June）
Survey on the contaminations of PFOS and related PFCs in Lake Biwa water (2009, Tsuda)
PFOS, PFOA level（2009 May, June）

20. A survey on pollution of organic PFCs in the area of Osaka Prefecture (2009, Uebori)
(2007年11-２０10年2月)調査事例
540-1,400
1,300
31,000 16
230
260
530
3.0
310
150,000
32,000
26,000 ① ② ④ ③ ⑫ ⑭ ⑧ ⑥ ⑪ ⑦ ⑤ ⑬ ⑨ ⑩
12,000
安威川
名神高速道路
東海道新幹線
阪急京都線
東海道線 淀川
阪急千里線
230
170
新御堂筋 国道
176 号線
京阪本線
　　河 川 地下水

21. pollution of organic PFCs in the area of Osaka Prefecture
Fluoro telomer (FTs) in air (2009, Uebori)
地点1
地点2
地点3
製造・使用事業場周辺環境の把握と対策の評価、 大気環境調査及び類縁化合物の実態把握（大阪府）
大気中テロマー類分析結果
地点4
地点5

22. Evaluation of occurrence of PFOS, PFOS and related compounds around the manufacturing facility (2009, Yamamoto, Tojo)
10μg/L
1μg/L
100ng/L
PFHxA
PFOA
PFOS
10ng/L
1ng/L
製造・使用事業場周辺環境におけるPFOS・PFOAおよびその類縁物質の実態把握と対策の評価（大阪市）

23. Temporal trend of PFCs of sea water in Osaka Bay (2009, Yagi)
concentration level of PFCs in coastal seawater in Kobe
Temporal trend of PFCs of sea water in Osaka Bay (2009, Yagi)
PFOA C8
PFOA
PFHxA C6
神戸沿岸海域地点表層水中のPFCs濃度の経年変化
(alternative)
PFHxA

24. PFC monitoring in coastal area using mussle (2009, NIES)

25. PFC monitoring in land area using drogonfly (2009, NIES)

26. national survey ～ global survey
summary
PFC monitoring using drogonfly
finding new source
トンボを用いた環境モニタリング
新たな汚染源の発見
全国調査～地球規模調査へ
national survey ～ global survey

27. Thank you for your attention
Acknowledgements
This research was supported by “Environment Technology Development Fund by the Ministry of the　Environment Japan ”
M-06 Study on sources, environmental level, and treatment technology of organofluoro compounds
M-06 Study on sources, environmental level, and treatment technology of organofluoro compounds
(Abstract of the Final Report）
Contact person Takeshi Nakano
Director, Environmental Safety division,
Hyogo Pref. Institute of Environmental Sciences
, Yukihira-cho, Suma-ku, Kobe Japan
TEL FAX
Total Budget for FY2008-FY ,060,000Yen (FY2009; 13,000,000Yen)
Key Words PFCs, Fluorotelomer, Isomer-specific analysis, Source estimation, Bioindicator
[Abstract]
In this study, the seven research institutes of national and local governments in Japan in which area high concentrations of the pollutants collaborated to elucidate pollution and sources of organofluoro compounds.
・Perfluorochemicals(PFCs) in river, lake, sea, and effluent water
Concentrations of perfluorohexanoic acid(PFHxA) as an alternative of perfluorooctanoic acid(PFOA) in the river and sea of Osaka area were observed. The PFOA level in surface water was decreased, and PFHxA level tended to be become higher. The concentrations were ng/L for perfluorooctane sulfonate (PFOS) and ng/L for PFOA in Lake Biwa in For the 31 rivers around Lake Biwa, those were ND-10 ng/L for PFOS and ND-32 ng/L for PFOA in In addition, several kinds of PFCs including PFOS were detected from one of the effluent water of a nonferrous metal manufacturing plant.
・Fluorotelomer compounds(FTs)
FTs is semivolatile compounds which indicate precursor of perfluoro carboxylic compounds (PFCAs). Various FTs were detected in commercialized organofluoro product. In addition, FTs which exist in the fluorinated polymer products are detected in ambient air. More over, Daily variation of PFCs including FTs in ambient air was observed.
・Monitoring of PFCs in land areas using bioindicators.
By the dragonfly monitoring, on the other hand, unexpectedly high levels of some of the compounds were found in rural areas with no particular industrial activities around the areas, suggesting presence of previously unidentified sources of these chemicals. The dragonfly monitoring will be promoted from nationwide to a global survey.
1.Introduction
Perfluorooctane sulfonate(PFOS) and related perfluorinated chemicals (PFCs) have become emerging persistent organic pollutants (POPs) in 2009, the potential emission sources of PFCs are not understood. The research aim was to investigate the situation of PFCs emissions from factories producing / using PFCs in the area of participated local governments and to establish measures to promptly respond to the issue. The project was jointly conducted by institutes of national and local governments in Japan in which area high concentrations of the pollutants have been observed.
2.Research Objective
(1) Understanding of the source and evaluation of transboundary pollution of fluorotelomer compounds(FTs).(Hyogo Prefetural Institute of Environmental Sciences)
(2) Survey on the contaminations of PFOS and related PFCs in Lake Biwa water (Lake Biwa Environmental Research Institute)
(3) A survey on pollution of organic PFCs in the area of Osaka Prefecture (Research Institute of Environment, Agriculture and Fisheries, Osaka Prefectural Government)
(4) Evaluation of occurrence of PFOS, PFOS and related compounds around the manufacturing facility. (Osaka City Institute of Public Health and Environmental Sciences)
(5) Concentration level of PFCs in coastal seawater in Kobe (Kobe Institute of Health)
(6) Survey of the PFCs level and the type of discharging industries (Tokyo Metropolitan Research Institute of Environmental Protection)
(7) Trend analysis of fluorosurfactants pollution by the archived samples in environmental specimen bank (National institute for environmental studies)
3. Research Method
(1) Identification and understanding of concentration patterns of FTs in Fluorinated oil and water repellents. An analysis of FTs in ambient air was examined. A survey of FTs, PFCAs and perfluoro- alkyl sulfonates(PFASs) in atmosphere was performed. Concentrations of FTs, PFCAs and PFASs in the yellow sand season were monitored.
(2) A survey was performed for levels and seasonal changes of PFOS and PFOA concentrations in surface water from Lake Biwa and rivers around Lake Biwa located in the most upper stream of Yodo River Basin. Analyses of PFOS and PFOA were performed by the method of Ministry of the Environment in Japan1).
(3) An environmental survey on the concentrations of PFCs and FTs in ambient air and water samples such as river, sea, and ground water was conducted. The components of PFOA and its related compounds in river and ground water samples were evaluated.
(4) Analysis of fluorotelomer alcohols(FTOHs) in air were done by high resolution GC/MS. Fundamental study on analytical methods for PFASs/PFCAs in ambient air was undertaken. Institutions of local government determined PFOS/PFOA levels in surface water in order to understand the pollutions of these compounds in Kansai Area. Isomer specific analytical methods for Per- and poly fluorinated alkyl substances such as PFOS/PFOA were developed and applied to environmental samples. Analysis of PFCAs (C2-C4) were carried out by IC/MS.
(5) In order to grasp concentration level by PFCs comprehensively, we investigated the current distribution and trends of concentration of PFCs in Osaka Bay. In addition we examined each step to find the most effective process for removing PFCs of wastewater treatment process.
(6) PFOS was detected at the highest concentration in the Tama River, compared with other rivers in Tokyo. The type of industry discharging PFCs has been surveyed through the sewers to the A sewage treatment plant (A STP) and B STP from 2008 to 2009.
(7) PFOS and other fluorosurfactants levels in bivalves and dragonflies were analyzed by the strong alkaline digestion method – LCMSMS combination2) in order to reveal spatial and temporal trends of their pollution in Japan.
4. Results and discussions
(1) Fluorinated oil and water repellents, considered FTs sources3), were analyzed using by head space GC/MS. As results, Various FTs such as FTOHs, Fluoroteomer acrylates(FTAcrylates), Fluorotelomer methacrylates(FTMethacrylates), Fluorotelomer olefins(FTOlefins, and Fluorotelomer Iodides(FTIs) were detected. Additionally, concentration pattern of FTs in the products which respond to PFOA problem was different, compared with conventional products. FTs which exist in the fluorinated polymer products are detected in ambient air. New method to measure the concentration of FTs was established that increased detection of target compounds and improved recovery rates. FTs, PFCAs, PFASs in atmosphere were investigated. As results, PFCs concentration patterns were different according to time and place. Part of PFCAs were detected with gas phase(Fig.1).
Fig.1　Gas phase and particle phase distribution of PFCs from atmospheric sample collected on the sampling point in summer.
　 　　 The concentrations of FTs, PFCAs and PFASs were monitored in the yellow sand season to evaluate of transboundary pollution derived from the continental china. The monitoring is continuing now.
(2) The concentrations were 0.8～5.3 ng/L for PFOS and 7.0～26 ng/L for PFOA in Lake Biwa (14 sites) from February to November in Seasonal changes were recognized for the PFOS and PFOA concentrations only in the 2 sites (8C and 168) of southern basin of Lake Biwa. For the 31 rivers (35 sites) around Lake Biwa, those were ND～10 ng/L for PFOS and ND～32 ng/L for PFOA in May and June , The highest concentrations, PFOS 10 ng/L and PFOA 32 ng/L, were detected in Moriyama River flowing into eastern area of southern basin of Lake Biwa.
(3) The concentrations of PFOA and PFOS in the river and sea area of Osaka Prefecture were at the same level in 2007 when the Osaka Prefecture Government had been conducted (Fig.2).
Fig.2　 The concentrations of PFOA and PFOS in the river and sea area
The high concentrations of PFHxA as an alternative of PFOA in some of the rivers were observed and its pollution spreaded into the sea area. The ratio of PFCs components in the river waters was roughly classified into two. The concentrations of PFCs and the ratio of their components in the ground water were different at the sampling sites, and these results indicate the contribution of individual emission source near the sites (Fig.3).
Fig.3 The concentrations of PFCs and the ratio of their components in the water samples
The concentrations of PFCs in ambient air varied daily. In order to understand the concentration of PFCs, it is important to investigate sampling methods such as sampling time, collection efficiencies on individual sampling materials and etc.
(4) High sensitivity for analysis of FTOHs using high resolution GC/MS was developed. To evaluate the recovery of PFASs/PFCAs, isotope-labeled standards were spiked in quartz-fiber filter. Recoveries of PFOS/PFOA, PFHxA, perfluorononanoic acid(PFNA), perfluorodecanoic acid(PFDA) and perfluorohexane sulfonate (PFHxS) were 100±30%. perfluorobutanoic acid(PFBA) and perfluorododecanoic acid(PFDoA) were not recovered. On the other hand, a breakthrough experiment was performed using high volume air sampler. PFASs/PFCAs including PFOS and PFOA were passed through a quartz-fiber filter in some situations. Comparing the previous investigations, the concentration of PFOA in surface water from Osaka area was decreased, and concentration of PFHxA tended to be become higher than PFOA in the several sampling sites. This realizes the replacement of C8 products (PFOA) with alternatives such as C6 products (PFHxA) in fluorochemical manufacture.
Homologue and isomers of PFOS/PFOA were detected in surface water samples(Fig.4), and the profiles were found to be different in several sampling sites. This result indicated that the profiles were available to reveal the source estimation of these compounds. A developed method of PFCAs (C2-C4) using IC/MS was applicable to water samples including seawater. The maximum of concentration of trifluoroacetic acid(C2) exceed 100ng/mL.
Fig.4 Isomer specific analysis for PFOS
(5) Concentration levels of PFCs were investigated in coastal seawater of Kobe from May 2004 to January 2010 using frozen seawater. In 2004, PFOA concentrations showed ng/L, and then the concentration was gradually decreasing. However, since August 2008 PFHxA　concentration began to increase, in August 2009 PFHxA concentration reached to about 500 ng/L(Fig.5). Perhaps those reason would be because fluoropolymer manufactures changed PFOA to alternatives PFHxA.
In addition, we found the most effective process for removing PFCs in each step of wastewater treatment was activated carbon treatment.
Fig.5 Trends of PFCs concentration in coastal seawater of Kobe
(6) Several kinds of PFCs including PFOS were detected from the drainage of a nonferrous metal manufacturing industry and so on (A STP). We analyzed the water sample of specific trunk and its branch sewers to B STP of which effluent PFOA was detected more than 100ng/L in Though, the concentration of PFOA decreased in influent and effluent water, PFNA whose chain length longer than PFOA was detected from one of the branch sewers. Then we analyzed the drainage discharged to the branch sewers, PFNA was detected more than 6,000ng/L from one of the academic organizations.
We analyzed effluent of 6 STPs flowing into the Tama River, and calculated the load of PFCs in As a result, it was clarified that the loads of PFOS and PFOA decreased in comparison with the data of 2005 greatly. The reason for this decrease of load, it is thought that there is the efforts for discharge reduction of PFCs with 2010/2015 PFOA Stewardship Program about PFOA and Stockholm Convention on POPs about PFOS.
(7) Relatively higher levels were found around heavily populated / industrialized areas, such as Tokyo and Osaka Bays. Their levels were also higher in some areas where suspected sources, such as factories producing / using PFCs, were located. Clear increasing trends were found in Japanese coastal environment in recent two decades. By the dragonfly monitoring, on the other hand, unexpectedly high levels of some of the compounds were found in rural areas with no particular industrial activities around the areas, suggesting presence of previously unidentified sources of these chemicals(Fig.6).
Fig.6 Environmental monitoring using dragonfly as biomarker
(PFOS, PFOA, PFNA, PFDA)
Thank you for your attention