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Transcript

Fate

of P

olyb

rom

inat

ed D

iphe

nyl E

ther

s Fa

te o

f Pol

ybro

min

ated

Dip

heny

l Eth

ers

(PBD

Es) i

n W

aste

wat

ers

(PBD

Es) i

n W

aste

wat

ers

Mar

k J.

La

Guar

dia

Mar

k J.

La

Guar

dia

Virgin

ia I

nst

itute

of

Mar

ine

Sci

ence

Virgin

ia I

nst

itute

of

Mar

ine

Sci

ence

Colle

ge

of

Will

iam

and M

ary

Colle

ge

of

Will

iam

and M

ary

Glo

uce

ster

Poin

t, V

irgin

iaG

louce

ster

Poin

t, V

irgin

iam

arkl

mar

kl@@

vim

svi

ms ..

edu

edu

Poly

brom

inat

ed D

iphe

nyl E

ther

s (P

BDEs

)Po

lybr

omin

ated

Dip

heny

l Eth

ers

(PBD

Es)

O

BrBrBr

Br

Br

Br

Br

BrBrBr

BD

E-2

09

O

Br

Br

Br

Br

Br

Br

Br

•Bro

min

ated

Flam

e-re

tard

ants

•G

lobal

2001 d

eman

d 6

7,3

90 m

etric

tons

(MT)

•Thre

e co

mm

erci

al f

orm

ula

tions

•D

eca-

BD

Es,

~80%

, pla

stic

s in

com

pute

rs,

TVs,

•O

cta-B

DEs,

~7%

, pla

stic

s…

•Pen

ta-B

DEs,

~13%

, poly

ure

than

e fo

am

s•

sim

ilar

IUPA

C n

amin

g s

chem

e as

PCBs

•98%

of

Penta

-use

d in N

ort

h A

mer

ica

BD

E-1

83

O

Br

Br

Br

Br

Br

BD

E-9

9

PBD

E Ex

posu

re

U.S.

bloo

d lev

els 19

73 a

nd 2

003

(pg/

g, lip

id wt

., n=

100)

Sc

hect

er e

t al.,

200

5

110100

1000

1000

0

1000

00

1000

000

Diox

ins

Dibe

nzof

uran

sCo

-Pla

nar P

CBs

Mon

o-Or

tho

PCBs

PBDE

s

pg/g (ppt)

1973

2003

Com

par

ison

Bet

wee

n C

once

ntr

atio

ns

of P

BD

Es

in B

reas

t M

ilk

fro

m N

orth

Am

eric

a an

d E

uro

pe

Sam

plin

g Y

ear

1975

1980

1985

1990

1995

2000

Concnetration (ng/g lipid weight)

050100

150

200

Nor

th A

mer

ica

Sw

eden

Fin

land

Sa

mp

les

co

lle

cte

d i

n

Au

sti

n &

De

nv

er

Sa

mp

les

co

lle

cte

d i

n N

ew

Yo

rk S

tate

Ca

na

dia

n

Mil

k B

an

k

Ca

na

dia

n

Mil

k B

an

k

4

Ca

nad

ian

Milk

Ba

nk

an

d N

ew

Yo

rk S

tate

fro

m R

yan

an

d P

atr

y 2

00

0,

De

nve

r an

d A

ust

in r

esu

lts

fro

m P

apke

et

al

20

01

; S

we

dis

h d

ata

fro

m M

eir

on

yte

Gu

vern

ius

an

d N

ore

n 2

00

1,

Fin

nis

h d

ata

fro

m S

tra

nd

ma

n e

t al

. 2

00

0

PBD

E Ex

posu

re

•Cla

ssic

PO

P g

lobal

red

istr

ibution

•D

etec

ted in:

US,

Euro

pea

n a

nd A

sian

fis

h,

Arc

tic

seals

, dee

p o

cean

s w

hal

es,

terr

estr

ial

birds/

eggs,

chic

kens,

…,

hum

ans

•PBD

Es

mim

ic t

hyr

oid

horm

ones

critica

l in

ea

rly

dev

elopm

ent

(mg/K

g (

ppm

), b

ody

wei

ght)

•PBD

Es

per

sist

ent

& b

ioac

cum

ula

te

•PBD

E r

estr

ictions/

legis

lation

•Pen

ta-

and

Oct

a-fo

rmula

tion

s

•2004,

ban f

rom

Euro

pea

n m

arke

ts

•2005,

volu

nta

ry p

roduct

ion h

alt

in t

he

US

Fish

Tis

sue

and

Sedi

men

t Con

tam

inan

ts

Fish

Tis

sue

and

Sedi

men

t Con

tam

inan

ts

Mon

itorin

g Pr

ogra

m

Mon

itorin

g Pr

ogra

m --

VA D

EQVA

DEQ

Virg

inia F

ish S

urve

y (To

tal-P

BDEs

)

0

100

200

300

400

500

050

100

150

200

250

300

350

Numb

er of

Sam

ples

mirco-g/Kg (wet wt.)

2000

Virg

inia F

ish S

urve

y (To

tal-P

BDEs

)

0

100

200

300

400

500

050

100

150

200

250

300

350

Numb

er of

Sam

ples

mirco-g/Kg (wet wt.)

2000

2001

Virg

inia

Fis

h Su

rvey

(Tot

al-P

BD

Es)

0

200

400

600

800

1000

1200

1400

1600

010

020

030

040

050

0N

umbe

r of S

ampl

es

mirco-g/Kg (wet wt.)

2000

2001

2002

2000 –

322 s

ample

s (6

9 n

d),

24 (

7%

) >

50µg/K

g,

max

. 417µg/K

g

2001 –

413 s

ample

s (6

7 n

d),

26 (

6%

) >

50µg/K

g,

max

. 220µg/K

g

2002 –

386 s

ample

s (2

4 n

d),

53 (

14%

) >

50µg/K

g,

max.

14

09

µg

/K

g

ww

w.d

eq

.vir

gin

ia.g

ov/

fish

tiss

ue/

ho

mep

ag

e.h

tml

Parti

tioni

ng o

f PBD

Es in

WW

TPPa

rtitio

ning

of P

BDEs

in W

WTP

Lit

tle R

iver

WW

TP

, W

ind

sor,

On

tari

o,

Can

ad

a

•an

aero

bic

dig

estion (

Dec

a-BD

Es)

•hal

f-liv

e ~

700 d

ays

(Ger

ecke

et a

l.,

(Chem

osp

her

e, 2

006)

•re

duct

ive

deb

rom

ination (

pro

duct

s nona-

and o

cta-

BD

Es

(Ger

ecke

et a

l.,

(ES&

T,

2005)

PBD

Es in

Effl

uent

& E

fflue

nt D

omin

ated

PB

DEs

in E

fflue

nt &

Effl

uent

Dom

inat

ed

Rec

eivi

ng S

tream

Rec

eivi

ng S

tream

Pent

a- (f

orm

ulat

ion)

BD

Es

02468101214

BD

E47

BD

E100

BD

E99

BD

E154

BD

E153

PBD

E co

ngen

ers

ng/L (ppt)

Efflu

ent

Stre

am

•PBD

Es

det

ecte

d in W

WTP e

fflu

ent

(ppt

to p

pb)

•lo

w n

g/L

(ppt)

for

Pen

ta-

•µg/L

(ppb)

leve

ls f

or

Dec

a-B

DEs

•Ass

oci

ated

with p

articl

es

•Sim

ilar

effluen

t an

d s

trea

m c

once

ntr

ations

•Eff

luen

t-dom

inat

ed s

trea

ms

•Tex

tile

& p

last

ics

indust

ries

pote

ntial

sourc

es t

o W

WTPs

•In

dust

rial

pre

trea

tmen

t (D

eca-

reduct

ion)

Dec

a- (f

orm

ulat

ion)

BD

Es

02,

000

4,00

06,

000

8,00

010

,000

12,0

0014

,000

BDE2

07BD

E206

BDE2

09

PBD

E co

ngen

ers

ng/L (ppt)

Efflu

ent

Stre

am

Pent

aPe

nta --

BDEs

BDEs

in R

ecei

ving

Stre

am

in R

ecei

ving

Stre

am

Sedi

men

ts fr

om a

WW

TP

Sedi

men

ts fr

om a

WW

TP

Penta

-BDEs

in Se

dimen

ts

01,0

002,0

003,0

004,0

005,0

006,0

007,0

00

-0.1

00.5

3.26.7

miles

from

outfa

ll

micro-g/kg (% TOC)

BDE4

7BD

E100

BDE9

9BD

E154

BDE1

53

•PBD

Es

(Pen

ta-)

incr

ease

d fro

m t

he

outf

all to

6.7

mile

s (<

7 µ

g/K

g,

dry

wt.

)

•Bio

ta (

min

now

s an

d s

unfish

) nea

r th

e outf

all

190 t

o 8

30 µ

g/K

g,

whole

body,

wet

wt.

Dec

aD

eca --

BDEs

BDEs

in a

WW

TP R

ecei

ving

Stre

am

in a

WW

TP R

ecei

ving

Stre

am

Sedi

men

tsSe

dim

ents

Dec

a-B

DE

s in

Sed

imen

ts

050

,000

100,

000

150,

000

200,

000

250,

000

300,

000

350,

000

-0.1

00.

53.

26.

7

mile

s fr

om o

utfa

ll

micro-g/kg (% TOC)

BD

E-20

9

BD

E-2

09

•D

eca-

BD

E (

curr

en

t u

se p

rod

uct

) det

ecte

d a

t th

e outf

all an

d u

p t

o 6

.7 m

iles

dow

n s

trea

m

•hig

hes

t at

0.5

mile

s (~

300 µ

g/k

g,

dry

wt.

)

•al

so B

DE-2

09 p

ote

ntial

deg

radat

ion p

roduct

s (p

pb,

dry

wt.

)

Pote

ntal

Dec

a- (B

DE-

209)

deg

rada

tion

prod

ucts

in s

edim

ents

110100

1,00

0

10,0

00

100,

000

-0.1

00.

53.

26.

7

mile

s fr

om o

utfa

ll

micro-g/kg (% TOC)

-197

-203

-196

-208

-207

-206

PBD

Es in

Sew

age

Slud

ge (B

ioso

lids)

PBD

Es in

Sew

age

Slud

ge (B

ioso

lids)

•Bio

solid

s, >

50%

(~

7 m

illio

n t

ons)

of

the

U.S

. se

wag

e sl

udge

is lan

d a

pplie

d

•cr

op/r

ange/

pas

ture

s la

nds,

fore

sts,

min

e si

te r

ecla

mat

ion a

nd

hom

e gar

den

s

•use

d a

s so

il co

nditio

ner

and f

ertiliz

er

•Sed

imen

tation is

an e

ssen

tial

ste

p in w

aste

wat

er t

reat

men

t

•re

sultin

g s

olid

s ar

e im

port

ant

sinks

for

the

rem

ova

l of

per

sist

ent

lipophili

c co

mpounds

•>

96%

of PB

DEs

rem

ove

d in s

ludge

(Nort

h,

et a

l.,

ES&

T 2

004)

PBD

E Bi

osol

id S

urve

y

Penta

-BDEs

in Bi

osoli

ds

050

010

0015

0020

0025

00

Compost-A

Compost-B

Compost-C

Lime-A

Lime-B

Heat-A

Heat-B

AD-A

AD-B

AD-C

AD-D

Stabil

izatio

n proc

ess

micro-g/kg (dry wt.)

BDE4

7BD

E100

BDE9

9BD

E154

BDE1

53

PBD

E Bi

osol

id S

urve

y

•Sam

ple

s (n

=11)

from

NY,

MD

, VA,

TX ,

CA

•Cla

ss B

(n=

7),

5-a

nae

robic

ally

sta

bili

zed,

2-

lime-

stab

ilize

d

•Cla

ss A

(n=

5)

3-c

om

post

ed,

and 2

-hea

t tr

eate

d/p

elle

tize

d

•100%

PBD

E d

etec

tion

•m

g/k

g (

ppm

) le

vels

•lo

cation o

r tr

eatm

ent

had

no e

ffec

t

R.C

Hale

et

al.

,2001

PBD

E Bi

osol

id S

urve

y (c

ont.)

PBD

E Bi

osol

id S

urve

y (c

ont.)

Deca

-BDE (

BDE-2

09) in

Bios

olids

010

0020

0030

0040

0050

00

Compost-A

Compost-B

Compost-C

Lime-A

Lime-B

Heat-A

Heat-B

AD-A

AD-B

AD-C

AD-D

Stabil

izatio

n proc

ess

micro-g/kg (dry wt.)

BDE2

09•

Bio

solid

s (n

=11)

from

NY,

MD

, VA,

TX,

CA

•100%

det

ection

•µg/k

g (

ppb)

to m

g/k

g (

ppm

) le

vels

•sp

ikes

may

indic

ate

indust

ry r

elea

ses

or

trea

tmen

t ef

fect

(?)

•D

eca-

BD

E c

urr

ent

use

BFR

•deb

rom

inat

ion (

?)

R.C

Hale

et

al.

,2001

Sour

ces

of P

BDEs

to w

aste

wat

er…

?So

urce

s of

PBD

Es to

was

tew

ater

…? ??

??

•PBD

Es

in foam

, fa

bric

&

carp

et b

acki

ng

•Exp

osu

re t

o U

V &

w

eath

er

•Fo

am y

ello

ws,

su

rfac

e fr

agm

ents

•PBD

Es

in h

ouse

dust

•ppb t

o p

pm

range

•dust

vs.

bre

ast

milk

, …

no c

orr

elat

ion

no c

orr

elat

ion

0

5,000

10,00

0

15,00

0

20,00

0

25,00

0

30,00

0

35,00

0

40,00

0

45,00

0

FLCA

1TX

CA2

CODC

MIW

AOR

MT

house dust (micro-g/kg, dw)

0100

200

300

400

500

600

700

800

breast milk (micro-g/kg, lw)

brea

st m

ilkho

useh

old

dust

May

200

4: h

ttp://

ww

w.e

wg.

org

Con

clus

ions

Con

clus

ions

•PB

DEs

det

ecte

d in ~

85%

of Virgin

ia’s

fis

h (

2001-2

003)

•~

9%

>50µg/K

g (

wet

wt.

)

•Sourc

e of PBD

E e

nvi

ronm

enta

l re

leas

es•

WW

TP

effluen

ts•

Eff

luen

t/Str

eam

s –

ppt

(ng/L

)•

Sed

imen

t –

ppb (

µg/K

g)

•Bio

ta –

ppm

(mg/K

g)

•P

BD

E a

re p

ers

iste

nt

an

d b

ioacc

um

ula

te

•Additio

nal

sourc

es…

???

•W

WTP s

olid

res

idual

s (B

ioso

lids)

-ppm

(mg/K

g)

•D

isca

rded

poly

mer

pro

duct

s•

House

hold

dust

–ppm

(mg/K

g)

…hum

an h

ealth c

once

rn…

???

•D

eca-

BD

E (

curr

ent

use

pro

duct

curr

ent

use

pro

duct

) m

ay d

egra

de

to low

er

bro

min

ated

PBD

Es,

incr

easi

ng b

ioav

aila

bili

ty a

nd t

oxi

city