Fate of Polybrominated Diphenyl Ethers (PBDEs) in … Guardia_Mid-Atlantic_06.… · Br Br Br Br Br...

14
Fate of Polybrominated Diphenyl Ethers Fate of Polybrominated Diphenyl Ethers (PBDEs) in Wastewaters (PBDEs) in Wastewaters Mark J. La Guardia Mark J. La Guardia Virginia Institute of Marine Science Virginia Institute of Marine Science College of William and Mary College of William and Mary Gloucester Point, Virginia Gloucester Point, Virginia markl markl @ @ vims vims . . edu edu

Transcript of Fate of Polybrominated Diphenyl Ethers (PBDEs) in … Guardia_Mid-Atlantic_06.… · Br Br Br Br Br...

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