POPs Problem Introduction (POPs problem) Perfluorinated compounds - - PowerPoint PPT Presentation

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POPs Problem Introduction (POPs problem) Perfluorinated compounds - - PowerPoint PPT Presentation

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March 10 (Mon) 2008, Bangkok Dr. Shigeo FUJII , Professor Graduate School of Global Environmental Studies, Kyoto University Todays Contents 1. 1. Introduction (POPs Problem) Introduction (POPs Problem) 2. 2. Perfluorinated Perfluorinated

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Shigeo Fujii, JST-Bangkok, March 10 2008

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  • Dr. Shigeo FUJII, Professor

Graduate School of Global Environmental Studies, Kyoto University

1.

  • 1. Introduction (POPs Problem)

Introduction (POPs Problem) 2.

  • 2. Perfluorinated

Perfluorinated Compounds (PFCs) Compounds (PFCs) 3.

  • 3. World Distribution

World Distribution 4.

  • 4. Their Sources and Effects of WTPs

Their Sources and Effects of WTPs 5.

  • 5. Countermeasures and Future

Countermeasures and Future Today’s Contents

March 10 (Mon) 2008, Bangkok

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Shigeo Fujii, JST-Bangkok, March 10 2008

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Persistent Organic Pollutants (POPs):

Chemical substances that persist in the environment, bioaccumulate through the food web, and pose a risk

  • f causing adverse effects to human health and the

environment. < UNEP> http:/ / www.chem.unep.ch/ pops/

POPs Problem

Three Key Properties:

>Persistency : never be reduced naturally (in biological and photolysis processes) > Bioaccumulation : low concentration in discharge high concentration in organisms > Risk : effects caused after long term contact (Toxicity recognition after a long period of usage)

Introduction (POPs problem)

Perfluorinated compounds (PFCs) World distribution Their sources and effects of WTPs Countermeasures and future

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Shigeo Fujii, JST-Bangkok, March 10 2008

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POPs Contamination

Type 4: POPs Contamination

Sources: Every place (manufacturers, users, consumers) Pollutants: POPs (Persistent organic pollutants) I nfluences: Increase of long-term risk to the public (sterility, feminization, endocrine disruption, cancer) Range: world-wide (including arctic circle) Measures: Ban of manufacture and use

Polluters = Victims Merits vs. Risk

Type 1: Hazardous material Discharge Type 2: Organic Pollution Type 3: Eutrophication

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Shigeo Fujii, JST-Bangkok, March 10 2008

4 A global treaty to protect human health and the environment from persistent organic pollutants (POPs). To outlaw nine* of the "dirty dozen" chemicals$, To limit the use of DDT to malaria control, To reduce unintentional production of Dioxins and Furans.

Parties to the convention have agreed to a process by which persistent toxic compounds can be reviewed and added to the convention, if they meet certain criteria for persistence and transboundary threat.

Stockholm Convention on Persistent Organic Pollutants (POPs)

* Aldrin, Endrin, Heptachior, HCB, Dieldrin, Chlodane, PCB, Toxaphenes, Mirex

$ nine* + DDT + Dioxins and Furans;

All of them are Chlorinated Cyclic Hydrocarbons

2001 May: Adoption 2004 May: Enforcement (ratification in 50 parties) Ratification: 128 parties

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Shigeo Fujii, JST-Bangkok, March 10 2008

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History of pollutants detected in the food-chain

Dioxin 80’s Chistoffer Rappe (Poly-chlorinated dibenzo-dioxins,

Defoliant (Viet Nam War), Incineration by-products)

O ( C l ) m ( C l ) n O

PCB 70’s Soren Jensen (Poly-chlorinated biphenyls,

Insultation oil)

( C l ) n ( C l ) m

PFOS 00’s 3M, John Giesy (Perfluoro-octane sulfonate,

Water repellent) C F

3

  • (

C F

2

)

6

  • C

F

2

S O

4

C l C l C l C l C l

DDT 60’s Rachel Carson (Silent Spring) (Dichloro-diphenyl-trichloro-ethane,

Insecticide)

PBDE 90’s Koidu Noren (Poly-brominated diphenyl-ehters,

Fire proofing agents)

( B r ) n ( B r ) m O

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Perfluorinated Compounds(PFCs)

CF3(CF2)n- Representative compounds

PFOS: Perfluoro-octane Sulfonate C8F17SO3

  • PFOA: Perfluoro-octane Acid

C8F15OO-

Unique Characteristics: hydrophobic & hydrophilic (oleophobic) water-repellent, non-stick materials Synthesized fully fluorinated compound, widely used in industrial and commercial applications since the 1960s.

Introduction (POPs problem)

Perfluorinated compounds (PFCs)

World distribution Their sources and effects of WTPs Countermeasures and future

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Applications and toxicity

PFOS: surface treatment, paper protection, performance chemical e.g. Scotchgard; Carpet; Cup & plate; Fire fighting foam; PFOA: intermediate, (salts:)emulsifier and surfactant e.g. Gore-Tex; Teflon (PTFE); Soap; Shampoo Toxicity: Peroxisome proliferation, Mitochondrial toxicity, Cell membrane disruption, Cancer of liver and spleen of rodents Endocrine Disrupter: I ncrease estrogen and decrease testosterone Decrease thyroid hormone levels

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Study on PFOS and PFOA

High PFOS concentration were detected in the blood of laborers 1 9 9 9 US EPA issued Harzardous Assessment of PFOA and its salts 2 3 OECD issued Harzardous Assessment of PFOS and its salts 2 2 3M Co. phased out manufacture and use of PFOS 2 Scotchgard (PFOS contained) was invented and manufactured. 1 9 5 6 C

  • n

t e n t Y e a r

2 5 5 7 5 1

  • 1

9 9 9 2 2 1 2 2 2 3 2 4 2 5 2 6

No of papers related PFOS/PFOA in a database (JDream II)

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Shigeo Fujii, JST-Bangkok, March 10 2008

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Range of Environmental Engineering

Bio-accumulation Bio-magnification Industries Commercial and Domestic Activities

Scope of the study

Food Drink Air Others Adverse effects: Carcinogen, Endocrine Disruption

Background

Their effects are not well understood

PFOS, PFOA

Drinking water Wastewater Surface water Treatment

Rarely reported Spatial distribution is not well understood (especially in developing countries) No Practical method

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2008/3/24

10

PFOS and PFOA are found in America, Europe and Japan, including environment (water, air, food), human health, and wild animals.

Surveys in the World

PFCs (Red) in Water Environment and PFCs (yellow) in animals, 2007 Our group Target Area

Introduction (POPs problem) Perfluorinated compounds (PFCs)

World distribution

Their sources and effects of WTPs Countermeasures and future

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Sampling areas ( :spot samples of tap water and surface water, :systematic survey)

Klang River

Asia North America Europe

Vancouver Calgary Orebro Johor Bahru Singapore Kota Kinabalu Bangkok Khon Kaen Rayong Hanoi

Penang

Taiwan

Yodo River

Shenzhen Khunming Hangzhou Istanbul

Kinki Chukoku

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Y=0.1X Y=10X Y=X 0.01 0.1 1 10 100 1000 10000 0.01 0.1 1 10 100 1000 10000 Yodo River Kota Kinabalu Phong River

PFOA

Y=0.1X Y=10X Y= X 0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000 Yodo R. Kota Kinabalu Phong River

PFOS

Results of repeated sampling and analysis at different periods

Concentrations fluctuated within one order of magnitude confirm concentration levels

  • I. Reproducibility of concentrations

Concentration (ng/ L) in a sampling period Concentration (ng/ L) in another sampling period

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0.01 0.1 1 10 100 1000 Orebro Kota Kinabalu Phong R. Hanoi Turkey Kinki Chao Phraya R. Johor Bahru Shenzhen Singapore Yodo River Concentration (ng/ L) 0.01 0.1 1 10 100 1000 Hanoi Kota Kinabalu Phong R. Orebro Turkey Kinki Chao Phraya R. Shenzhen Yodo R. Singapore Johor Barhu Concentration (ng/ L)

Concentrations in environmental waters

75% percentile 25% percentile Median Max Min

PFOS PFOA

21,000 < LOQ < LOQ

90% 85% PFOS (PFOA) were detected in majority of samples Concentrations fluctuated largely

N =12 N =21 N =29 N =12 N =04 N =15 N =15 N =09 N =34 N =24 N =06

High High Medium Medium Low Low High High Medium Medium Low Low

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0.01 0.1 1 10 100 1000 Orebro Kota Kinabalu Phong R. Hanoi Vancouver Istanbul Chao Phraya R. Johor Bahru Shenzhen Yodo River Hangzhou Concentration (ng/L)

PFOA

0.01 0.1 1 10 100 1000 Vancouver Hanoi Kota Kinabalu Phong River Orebro Turkey Chao Phraya R. Hangzhou Shenzhen Yodo River Johor Bahru Concentration (ng/L)

PFOS

Tap water concentration

Safety levels recommended by Minnesota State (U.S.A.) +25% increase in human blood concentrations (Harada et al. 2003) 300 ng/L 500 ng/L 50 ng/L

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Tap water vs surface water

PFOS

NE Y=5X Y=(1 /5)X IS JO HN OR CH KK PH YO VC HZ SH y = 0.74x R = 0.47

0.01 0.1 1 10 100 0.01 0.1 1 10 100 PFOA

Y=5X Y=(1 /5)X JO SH HN OR CH KK PH YO VC HZ TR NE y = 0.91x R = 0.84

0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000

Surface water concentration (ng/ L) Surface water concentration (ng/ L) Tap water concentration (ng/ L) Tap water concentration (ng/ L)

YO : Yodo R. CH : Bangkok SH : Shenzhen KK : Kota Kinablu PH : Khon Kean HN : Hanoi OR : Orebro JO : Johor Bahru IS : Istanbul NE : Nevshehir VC : Vancouver HZ : Hangzhou

Concentrations in tap waters ~ in environmental waters: SI MI LAR! Concentrations in tap waters ~ in environmental waters: SI MI LAR!

Water sources?

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Water supply source - tap water

Concentration in Concentration in water sources (ng/ L) sources (ng/ L) PFOS y = 1.1x R 2 = 0.8 0.1 1 10 100 0.1 1 10 100 Kinki, Japan Istanbul, Turkey PFOA y = 0.8x R 2 = 0.8 0.1 1 10 100 0.1 1 10 100 Kinki, Japan Istanbul, Turkey Concentration in tap water (ng/ L)

Increasing trend of tap water concentrations versus water source concentrations In general, PFOS and PFOA could not be effectively removed from water treatment steps. Increasing trend of tap water concentrations versus water source concentrations In general, PFOS and PFOA could not be effectively removed from water treatment steps.

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0.01 0.1 1 10 100 1000 10000 100000

Orebro Turkey Chao Phraya R. Shenzhen Singapore Yodo R. Concentration (ng/L)

0.01 0.1 1 10 100 1000 10000 100000

Orebro Turkey Chao Phraya R. Shenzhen Yodo R. Singapore

WWTP discharges

PFOS PFOA

WWTP discharges

  • ften had higher

concentrations than environmental water did.

0.01 0.1 1 10 100 1000 10000 100000

Orebro Turkey Chao Phraya R. Shenzhen Singapore Yodo R. Concentration (ng/L)

0.01 0.1 1 10 100 1000 10000 100000

Orebro Turkey Chao Phraya R. Shenzhen Yodo R. Singapore

WWTP discharges Surface water

N =02 N =01 N =01 N =01 N =10 N =10

Concentration (ng/ L)

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Mass balance

G. UJ - UJ - 13

Yodo R.

Uji R. Kizu R. Katsura R.

KZ -11

0% 100% Flowrate Chloride PFOS PFOA Flowrate Chloride PFOS PFOA Flowrate Chloride PFOS PFOA Nov-04 Mar-05 Nov-05

Mass flux contribution from upstream to Hirakata Bridge Hirakata Bridge

Good balance reflects no sink or rise of pollutants during transportation (Reference: BOD is reduced to 1/3)

(100% )

Introduction (POPs problem) Perfluorinated compounds (PFCs) World distribution

Their sources and effects of WTPs

Countermeasures and future

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G. UJ -

Uji R. Kizu R. Katsura R.

Contribution of WWTPs to Katsura River

WWTP 9 WWTP (7+8) WWTP 6

500,000 1,000,000 1,500,000 2,000,000 2,500,000 m3/d

WWTPs Katsura River

Flow

5 10 15 20 25 g/d

WWTPs Katsura River

PFOS

20 40 60 80 100 120 140 g/d

WWTPs Katsura River

PFOA

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Wastewater Treatment Plant Survey

Japan (11), Singapore (4), China (1), Turkey (1)

1 1 1 1

P F H x S P F O S P F H p A P F O A P F N A P F D A P F U n D A P F D

  • D

A C

  • n

c e n t r a t i

  • n

( n g / L ) P F H x S P F O S P F H p A P F O A P F N A P F D A P F U n D A P F D

  • D

A

N/A

M e d i a n A v e . M a x M i n

I n f l u e n t E f f u e n t

N/A

No obvious removal in WWTPs

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Mass flux of total PFCs

1000 2000 3000 4000 5000 Inf PC AS RS SC SF O3 BF Eff PFC conc.(ng/L)

Particulate Phase Aqueous Phase

total PFCs

1. 60% of total PFCs in influent was attached on particulate phase. 2. PFCs accumulated in activated sludge and circulated with return sludge 3. PFCs were not removed effectively. Ozone, BAC filter can not remove total PFCs. 4. 20% of total PFCs, or 50% of aqueous PFCs, were discharged to environment.

151(212) : aqueous (particulate ) for WWTP 21 (29) : aqueous (particulate ) for series 4 : particulate phase, 10 g/day : aqueous phase, 10 g/day : aqueous phase, 1 g/day

17 (146)

: aqueous (particulate ) in aeration tank

(1.4)

SF

1.1

PC AS SC

21 (29) 15 (9)

17 (146)

8 5 (60) 10 1.1 1.2

O3 BF

total-PFC

151(212) 69

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Mechanism of Mass Flows and PFCs Risk

Point sources <manufacturing

factory,

application factory,

consumers (people)>

Non-point sources Downstream Intake Water purification plant

No reduction negligible

Wastewater treatment plant Water Environment (Rivers, lakes) Tap water (people) (no removal) (no removal) <Risk>

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Possible Treatment

Biological Treatment

No decomposition is expected

Physical treatment

Activated Carbon Adsorption: can remove to some extent Membrane Filtration: Only RO is effective

Chemical Treatment

UV Irradiation: effective for PFOA with long time Ozonation: not effective Super/ Sub critical water: effective Chemical oxidation: Potassium persulfate is effective for PFOA

Introduction (POPs problem) Perfluorinated compounds (PFCs) World distribution Their sources and effects of WTPs

Countermeasures and future

When I started this research, PFOS was said to be tolerant to 1000oC Inciniration, but…. Still no practical method

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Practical Measures

In 2006, USEPA requested major PFOA

manufacturing companies to phase out PFOA Product ty 2015.

In 2008, EU will exclude good

containing FPOS more than 0.005Wt％ from markets.

In 2008, COP4 of POPs convention will

consider inclusion of PFOS in the list.

Still only PFOS and PFOA!!

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  • C. Polopasert, C. Visu, SB Kitpati, W

Wirojanagud (Thailand), NPH Lien, HT Hai (Vietnam), A Anton, M Mohamed, M Pauzi (Malaysia), JY Hu (Singapore), Y Guan, T Mizuno (China), Y.H.Liou (Taiwan), G. Lindstrom (Sweeden), R. Tasli (Turkey)

Thank you/あり がと う /ขอบคุณครับ

fujii@eden.env.kyoto-u.ac.jp

Acknowledgement

Akio Koizumi (Prof. Medicine of KU) S Tanaka (Ass. Prof.), Y Qiu, NPH Lien, M Nozoe, C Kunacheva,K Kimura, H Oyama, D Ikeda, STM Senevirathna