Con

gene

r spe

cific

pol

ybro

min

ated

diph

enyl

ethe

r (PB

DE)

id

entif

icat

ion

of fo

ur te

chni

cal f

lam

e-re

tard

ant m

ixtu

res,

D

E-71

, Bro

mka

l70-

5DE,

DE-

79 a

nd B

rom

kal7

9-8D

EM

. J. L

a G

uard

ia*,

R. C

. Hal

e an

d E.

Har

vey

Intr

oduc

tion

•Pr

evio

us s

tudi

es h

ave

docu

men

ted

the

maj

or P

BD

E co

ngen

ers

with

in

tech

nica

l PB

DE-

mix

ture

s (e

.g. D

E-71

), bu

t few

hav

e fo

cuse

d on

thei

r min

or

cons

titue

nts

•Th

ese

maj

or P

BD

Es c

onge

ners

(e.g

. BD

E-47

and

–99

) hav

e sh

own

to b

e ub

iqui

tous

, bio

accu

mul

ativ

een

docr

ine

disr

upto

rs, w

hich

has

lead

to a

hal

t in

thei

r pro

duct

ion

•H

ighe

r bro

min

ated

PBD

Es (e

.g. B

DE-

209)

, stil

l in

prod

uctio

n, a

re n

ot a

s w

idel

y di

strib

uted

in th

e en

viro

nmen

t and

hav

e lo

w b

iolo

gica

l effe

cts

•H

owev

er, t

hey

may

debr

omin

ate

to lo

wer

brom

inat

edPB

DEs

, in

crea

sing

thei

r bur

den

on th

e en

viro

nmen

t

•N

ew re

port

s no

w s

how

a la

rger

sui

te o

f PB

DEs

(tri-

thro

ugh

hept

a-B

DEs

) al

so u

biqu

itous

and

sus

pect

ed e

ndoc

rine

disr

upto

rs

Intr

oduc

tion

•Th

eref

ore,

a fu

ll ra

nge

of c

onst

ituen

ts o

f the

tech

nica

l mix

ture

s m

ust

then

be

unde

rsto

od to

iden

tify;

•po

ssib

le m

ixtu

re c

onta

min

ants

•de

grad

atio

n pr

oduc

ts o

f –20

9

•an

d so

urce

s of

acc

umul

ated

PB

DE

burd

ens

O

Br

Br

Br

Br

(Lite

ratu

re s

earc

h) 4

5PB

DEs

con

gene

rs p

revi

ousl

y re

port

ed in

co

mm

erci

al m

ixtu

res

or e

nviro

nmen

tal m

atrix

es -209

-209

-209

-119

-205

-205

-97/

-118

-120

-208

-208

-208

-101

-207

-207

-207

-100

-100

-206

-206

-206

-99

-99

-204

-204

-85

-85

-203

-203

-77

-197

-197

-75

-196

-196

-74

-191

-71

-190

-173

/-190

-66

-66

-184

-49

-49

-183

-183

-183

-47

-47

-181

-181

-37

-166

-35

-155

-155

-33

-28/

-33

-154

-154

-154

-32

-153

-153

-153

-28

-28/

-33

-140

-17

BD

E-17

-139

-139

-15

-138

-138

-7

*Mat

rixes

Dec

a-O

cta-

Pent

a-*M

atrix

esD

eca-

Oct

a-Pe

nta-

* mat

rixes

: air,

wat

er, s

ewag

e ef

fluen

t, se

dim

ents

, fis

h, b

ird e

ggs,

hu

man

blo

od, …

, (re

fere

nces

=18)

Sam

ples

and

Sta

ndar

ds•S

ampl

es (P

enta

-&O

cta-

BD

Es):

•D

E-71

& D

E-79

(Gre

at L

akes

C

hem

. USA

)

•B

rom

kal7

0-5D

E &

79-

8DE

(Che

mis

che

Fabr

ik K

alk

Gm

bH,

Ger

man

y)

•Sta

ndar

ds:

•57

PBD

Es c

onge

ners

, (A

ccuS

tand

ard,

Inc.

, Cam

brid

ge

Isot

ope

Labs

, Inc

., W

ellin

gton

Lab

s)•m

ono-

deca

-BD

Es

•Inc

lude

s 45

con

gene

rs fr

om o

ur

liter

atur

e se

arch

Ana

lytic

al M

etho

d•G

C: 6

890N

, (A

gile

ntTe

ch.,

USA

)•D

B-5

HT,

(30m

, 0.2

5mm

ID, 0

.1µm

film

) (A

gile

nt),

run

time

35 m

inut

es

•on-

colu

mn

inje

ctor

with

ove

n te

mp.

tr

acki

ng •ana

lytic

al: 5

5 –

300

o C

•bak

e-ou

t: 35

0 o C

, 5m

ins.

•R

eten

tion

time

inde

x (R

RI)

•M

arke

rs:p

enta

chlo

robe

nzen

e,

deca

chlo

rodi

phen

yl e

ther

and

BD

E-20

9

JEO

L, G

CM

ateI

I

•M

S:G

CM

ate

II (J

EOL

Ltd.

Jap

an),

benc

h-to

p do

uble

-focu

sing

mag

netic

se

ctor

MS

•EC

NI-S

IM (r

-gas

: met

hane

): [B

r]- 7

9, 8

1m/z

•QL:

mon

oBD

E–

nona

BD

Es1p

g,de

caB

DE

10pg

, on-

colu

mn

•EI:

200

to 1

000

m/z

, [M

]+, [

M-2

Br]

+

•EC

NI:

30 to

550

m/z

, fra

gmen

ts c

leav

ed a

t th

e et

her b

ond

(e.g

. [C

6Br 5

O]- )

on-c

olum

n ne

edle

PBD

Es, 5

7 A

naly

tical

Sta

ndar

ds,

(6-1

7 m

ins)

DB

-5H

T, (3

0m, 0

.25m

m ID

, 0.1

µm fi

lm)

643.

6

563.

6

PBD

Es, 5

7 A

naly

tical

Sta

ndar

ds (1

7-34

min

s)D

B-5

HT,

(30m

, 0.2

5mm

ID, 0

.1µm

film

)

PBD

E St

ruct

ural

Con

form

atio

n (B

DE-

209)

958.

1

799.

4

[M –

2Br]

-

[M]-

O

Br

Br

Br

Br

Br

Br

BrBr

Br

Br

O-

Br 5O

Br

Br

Br

Br

Br

Br

BrBr

Br

Br

Elec

tron

ioni

zatio

n (E

I)El

ectr

on C

aptu

re N

egat

ive

Ioni

zatio

n (E

CN

I)

ECN

I Mas

s Sp

ectr

a (B

DE-

201,

-204

)

O-

Br 4

O

Br

Br

Br

BrBr

Br

BrBr

BD

E-20

1

O-

Br 5

O

Br

BrBr

Br

Br

Br

Br

Br

O-

Br 3BD

E-20

4

Elec

tron

Cap

ture

Neg

ativ

e Io

niza

tion

(EC

NI)

DE-

71, E

CN

I-SIM

Chr

omat

ogra

ms

(79,

81 m

/z)

BD

E-47

-100

-99 -8

5-1

54-1

53

-47(

-74)

-100

-99

-85

-154

-153

-17

-75

-49

-28/

33

-71

-66

-97

-126/155

-139

-138

-175

/183

-140

tetr

a-a

tetr

a-b

pent

a-b

pent

a-a

(x25

)

Bro

mka

l70-

5de,

EC

NI-S

IM C

hrom

atog

ram

s (7

9, 8

1 m

/z)

BD

E-47

-100

-99

-85

-154

-153

-99

-100

-47(

-74)

-85

-154

-153

(x25

)

-17

-28/

33-7

5

-49

-66

tetr

a-b

-97

-126/155

-139

-138

-140

-175

/183

% C

ompo

sitio

n Pe

nta-

form

ulat

ions

0102030405060

-99

-47

-100

-153

-154

-85

-139

-49

-138

-66

-28/-33

-155

-140

penta-b

-175/-183

-17

penta-a

-75

-71

-97

tetra-a

tetra-b

% Composition

DE-7

1B7

0-5D

E

0

0.2

0.4

0.6

0.81

-139-49-138-66-28/-33-155-140penta-b-175/-183-17penta-a-75-71-97tetra-atetra-b

% Composition

DE

-71

B70

-5D

E

(*<0

.02%

) **

***

*

DE-

79, E

CN

I-SIM

Chr

omat

ogra

ms

(79,

81

m/z

)

-207

-153

-197

-175

/183

-154

-203 -196

-201

-207

-196

-197

-203

-201

-153

-154

-175

/183

hepta-a -191

-173/190

-208

-206

-138-140

-144

hexa

-a

-184

-209

(x25

)he

xa-b

Bro

mka

l79-

8de,

EC

NI-S

IM C

hrom

atog

ram

s (7

9, 8

1 m

/z)

-207

-206

-209

-197 -203 -1

96

-175

/183

-153

-208

-207

-206

-209

-201

-197 -203

-196

-154

-144

-184

-173/190

-175

/183

(x25

)

% C

ompo

sitio

n O

cta-

form

ulat

ions

01020304050

-175/-183

-197

-207

-196

-153

-203

-173/-190

hepta-a

-206

-209

-154

-201

-138

-128

-208

-144

-140

-191

-184

hexa-a

hexa-b

% Composition

DE-7

9B7

9-8D

E

0.15

0.17

0

0.2

0.4

0.6

0.81

1.2

-154

-201

-138

-128

-208

-144

-140

-191

-184

hexa-a

hexa-b

% Composition

DE-

79B

79-8

DE

**

**

**

(* <

0.0

2%) *

*

Con

clus

ions

•GC

/MS

met

hod

for t

he id

entif

icat

ion

of 5

7 PB

DEs

–R

eten

tion

time

inde

x (R

RI)

•30

m (D

B-5

HT)

, chr

omat

ogra

phic

ally

sep

arat

ed 4

5 co

ngen

ers,

6-p

airs

co-

elut

ed

–St

ruct

ural

con

form

atio

n by

ion

frag

men

tatio

n m

onito

ring:

•EI

, [M

]+, [

M-2

Br]

+

•EC

NI,

[cle

avin

g of

the

ethe

r bon

d]-(id

entif

ies

diet

herr

ing

brom

ine

subs

titut

ion)

•Pen

ta-m

ixtu

res

cont

aine

d 22

PB

DE

cong

ener

s–

Prev

ious

ly u

nrep

orte

d co

ngen

ers:

•

BD

E-71

, 75

•2,

pent

a-an

d 2,

tetr

a-B

DEs

hom

olog

ues

–N

ot id

entif

ied

in th

is s

tudy

: BD

E-10

1–

BD

E-74

and

–47

unr

esol

ved

due

to th

e hi

gh c

once

ntra

tion

of –

47•

Sepa

ratio

n re

quire

s a

60m

col

umn

Con

clus

ions

•Oct

a-m

ixtu

res

cont

aine

d 21

con

gene

rs–

Prev

ious

ly u

nrep

orte

d co

ngen

ers:

•B

DE-

128,

138

, -14

0, -1

44, -

184,

-201

•2,

hexa

-and

1, h

epta

-BD

E ho

mol

ogue

s

–N

ot id

entif

ied

in th

is s

tudy

: BD

E-18

1, -2

04 a

nd –

205

•B

DE-

204

or -2

01…

???

•A to

tal o

f 36

PBD

Es w

ere

iden

tifie

d w

ithin

the

Pent

a-an

d O

cta-

form

ulat

ions

–ho

wev

er, t

he s

ourc

e of

10

PBD

Es p

revi

ousl

y re

port

ed in

en

viro

nmen

tal m

atrix

es a

re s

till u

nacc

ount

ed…