Graduate School of Global Environmental Studies, Kyoto ...

Shigeo Fujii, JST-Bangkok, March 10 20081

Dr. Shigeo FUJII, Professor

Graduate School of Global Environmental Studies,Kyoto University

1. Introduction (POPs Problem)2. Perfluorinated Compounds (PFCs)3. World Distribution4. Their Sources and Effects of WTPs5. Countermeasures and Future

Today’s Contents

March 10 (Mon) 2008, Bangkok


Persistent Organic Pollutants (POPs):Chemical substances that persist in the environment, bioaccumulate through the food web, and pose a riskof 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 WTPsCountermeasures and future


POPs Contamination

Type 4: POPs Contamination

Sources: Every place (manufacturers, users, consumers) Pollutants: POPs (Persistent organic pollutants) Influences: 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 = VictimsMerits vs. Risk

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


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: Adoption2004 May: Enforcement (ratification in 50 parties)Ratification: 128 parties


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(Cl)m (Cl)n

O

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

Insultation oil)(Cl)n(Cl)m

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

CF3-(CF2)6-CF2SO4

Cl

Cl

Cl

Cl ClDDT 60’s Rachel Carson (Silent Spring)(Dichloro-diphenyl-trichloro-ethane,Insecticide)

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

Fire proofing agents) (Br)n(Br)m

O


PerfluorinatedCompounds(PFCs)

CF3(CF2)n-

Representative compoundsPFOS: 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.




Applications and toxicityPFOS: surface treatment, paper protection, performance

chemicale.g. Scotchgard; Carpet; Cup & plate; Fire fighting foam;

PFOA: intermediate, (salts:)emulsifier and surfactante.g. Gore-Tex; Teflon (PTFE); Soap; Shampoo

Toxicity: Peroxisome proliferation, Mitochondrial toxicity, Cell membrane disruption, Cancer of liver and spleen of rodentsEndocrine Disrupter: Increase estrogen and decrease testosterone Decrease thyroid hormone levels


Study on PFOS and PFOA

High PFOS concentration were detected in the blood of laborers1999

US EPA issued Harzardous Assessment of PFOA and its salts2003

OECD issued Harzardous Assessment of PFOS and its salts2002

3M Co. phased out manufacture and use of PFOS2000

Scotchgard (PFOS contained) was invented and manufactured.1956

ContentYear

0 25 50 75 100

-19992000200120022003200420052006

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


Range of Environmental Engineering

Bio-accumulationBio-magnification

Industries Commercial and Domestic Activities

Scope of the study

Food

DrinkAir

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

Shigeo Fujii, JST-Bangkok, March 10 2008102008/3/24 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 groupTarget Area




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

Klang River

Asia

North America

Europe

Vancouver

Calgary

Orebro

Johor BahruSingapore

Kota Kinabalu

BangkokKhon Kaen

Rayong

Hanoi

Penang

Taiwan

YodoRiver

ShenzhenKhunming

Hangzhou

Istanbul

KinkiChukoku


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 RiverKota KinabaluPhong 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 KinabaluPhong 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


0.01

0.1

1

10

100

1000

Ore

bro

Kota

Kin

abal

uPh

ong

R.

Han

oi

Turk

eyKi

nki

Chao

Phr

aya

R.

Joho

r Ba

hru

Shen

zhen

Sing

apor

eYo

do R

iver

Con

cent

rati

on (

ng/L

)

0.01

0.1

1

10

100

1000

Han

oiKo

ta K

inab

alu

Phon

g R

.O

rebr

oTu

rkey

Kink

iCh

ao P

hray

a R

.Sh

enzh

enYo

do R

.Si

ngap

ore

Joho

r Ba

rhu

Con

cent

rati

on (

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 =

12N

=21

N =

29N

=12

N =

04N

=15

N =

15N

=09

N =

34N

=24

N =

06

HighHigh

MediumMedium

LowLow

HighHigh

MediumMedium

LowLow


0.01

0.1

1

10

100

1000

Ore

bro

Kota

Kin

abal

uPh

ong

R.

Han

oiVa

ncou

ver

Ista

nbul

Chao

Phr

aya

R.

Joho

r Ba

hru

Shen

zhen

Yodo

Riv

erH

angz

hou

Conc

entr

atio

n (n

g/L) PFOA

0.01

0.1

1

10

100

1000Va

ncou

ver

Han

oiKo

ta K

inab

alu

Phon

g R

iver

Ore

bro

Turk

eyCh

ao P

hray

a R

.H

angz

hou

Shen

zhen

Yodo

Riv

erJo

hor

Bahr

u

Conc

entr

atio

n (n

g/L) PFOS

Tap water concentration

Safety levels recommendedby Minnesota State (U.S.A.)

+25% increase in human blood concentrations (Harada et al.2003)

300 ng/L 500 ng/L

50 ng/L


Tap water vssurface water

PFOS

NE

Y=5X

Y=(1/5)X

IS

JO

HN

OR

CH

KK

PH

YO

VC

HZ

SHy = 0.74xR = 0.47

0.01

0.1

1

10

100

0.01 0.1 1 10 100

PFOAY=5X

Y=(1/5)XJO

SH

HN

OR

CH

KK

PH

YO

VC

HZ

TR

NE

y = 0 .91xR = 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 : BangkokSH : ShenzhenKK : Kota KinabluPH : Khon KeanHN : Hanoi

OR : OrebroJO : Johor BahruIS : IstanbulNE : NevshehirVC : VancouverHZ : Hangzhou

Concentrations in tap waters ~ in environmental waters: SIMILAR!Concentrations in tap waters ~ in environmental waters: SIMILAR!

Water sources?


Water supply source - tap water

Concentration in Concentration in water sources (ng/L)sources (ng/L)

PFOS

y = 1.1xR 2 = 0.8

0.1

1

10

100

0.1 1 10 100

Kinki, JapanIstanbul, Turkey

PFOA

y = 0.8xR 2 = 0.8

0.1

1

10

100

0.1 1 10 100

Kinki, JapanIstanbul, 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.


0.01

0.1

1

10

100

1000

10000

100000

Ore

bro

Turk

ey

Cha

o Ph

raya

R.

Shen

zhen

Sing

apor

e

Yodo

R.

Con

cent

ratio

n (n

g/L)

0.01

0.1

1

10

100

1000

10000

100000

Ore

bro

Turk

ey

Cha

o Ph

raya

R.

Shen

zhen

Yodo

R.

Sing

apor

e

WWTP dischargesPFOS PFOA

WWTP discharges often had higher concentrations than environmental water did.

0.01

0.1

1

10

100

1000

10000

100000

Ore

bro

Turk

ey

Cha

o Ph

raya

R.

Shen

zhen

Sing

apor

e

Yodo

R.

Con

cent

ratio

n (n

g/L)

0.01

0.1

1

10

100

1000

10000

100000

Ore

bro

Turk

ey

Cha

o Ph

raya

R.

Shen

zhen

Yodo

R.

Sing

apor

e

WWTP dischargesSurface water

N =

02

N =

01

N =

01

N =

01

N =

10

N =

10

Con

cen

trat

ion

(n

g/L)


Mass balance

G.

UJ -

UJ - 13

Yodo R.

Uji R.

Kizu R.

Katsura R.

KZ -11

0%

100%

Flow

rate

Chlo

ride

PFO

SPF

OA

Flow

rate

Chlo

ride

PFO

SPF

OA

Flow

rate

Chlo

ride

PFO

SPF

OA

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 distributionTheir sources and effects of WTPsCountermeasures and future


G.

UJ -

Uji R.

Kizu R.

Katsura R.

Contribution of WWTPs to Katsura River

WWTP 9

WWTP (7+8)

WWTP 6

0

500,000

1,000,000

1,500,000

2,000,000

2,500,000

m3/

d

WWTPs KatsuraRiver

Flow

0

5

10

15

20

25

g/d

WWTPs KatsuraRiver

PFOS

0

20

40

60

80

100

120

140

g/d

WWTPs KatsuraRiver

PFOA


Wastewater Treatment Plant SurveyJapan (11), Singapore (4), China (1), Turkey (1)

1

10

100

1000PFHxS

PFOS

PFHpA

PFOA

PFNA

PFDA

PFUnDA

PFDoDA

Concentration (ng/L)

PFHxS

PFOS

PFHpA

PFOA

PFNA

PFDA

PFUnDA

PFDoDA

N/A

MedianAve.

Max

Min

Influent Effuent

N/A

No obvious removal in WWTPs


Mass flux of total PFCs

0

1000

2000

3000

4000

5000

Inf

PC AS RS

SC SF O3

BF

Eff

PFC

con

c.(n

g/L)

Particulate PhaseAqueous 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/day17 (146) : aqueous (particulate ) in aeration tank

(1.4)

SF

1.1

PC AS SC

21 (29)

15 (9)

17 (146)

8

5 (60)

10

1.11.2O3 BF

total-PFC

151(212)69


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>


Possible Treatment

Biological TreatmentNo decomposition is expected

Physical treatmentActivated Carbon Adsorption: can remove to some extentMembrane Filtration: Only RO is effective

Chemical TreatmentUV Irradiation: effective for PFOA with long time Ozonation: not effectiveSuper/ Sub critical water: effectiveChemical oxidation: Potassium persulfate is effective for PFOA



When I started this research, PFOS was said to be tolerant to 1000oC Inciniration, but….

Still no practical method


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!!


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[email protected]

AcknowledgementAkio 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

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