9-8DE 7 ther (PBDE) identification of four technical flame ... Guardia_BFR_05.pdf · M. J. La...
Transcript of 9-8DE 7 ther (PBDE) identification of four technical flame ... Guardia_BFR_05.pdf · M. J. La...
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
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…