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17
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3 2
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62
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65
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6 8
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19
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3
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3
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C
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5 1
F i g
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3
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C
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3
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s
f
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T C D D
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5 7
F
i g
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B
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t
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sf
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a nd
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F
5 8
F i g
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3
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p
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d
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t
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o
f R R F
s
f
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H
x
C D D
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59
F i g
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3
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6
D
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F i g
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6
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o n of i
o n-m
o
l
e c ul
ei
nt
e r ac ti
o n si
nt
h
e
g
as
p h
a s e ,a n
d i
n v e st
i g
at
i
o n of i
n c r e a s ed
s el
e ct
i
vi
t
y f
o rt
a rg
et
ed
c
om p
o ne
nt a
n al y
si
s
(M
cL
a
f f
e rt
y
,19 83
)
.O
n et
y p
e of
M
S/
M
S
e
xp
e
ri m
e
nt
,o
na
b
e a
m i
n st
r um
e nt
,i
s
p
e
rf
o rm
e
d b y
s
e
l
e ct
i
ng t
h
ep
a r e nt
i
o ni
nt
h
efi
r st
st
ag
e of
a n al y
si
s, a nd
th
e n a n al y
zi
ng
t
h
ep
r od
u ct
i
o
n(
s
)
i
n t
h
e s e c o nd
s t
ag
e o
f
a
na
l y
si
s
(
B
u sc
h
,19 8 8
)
.E
a c
h
o
f
t
h
em
a s s a
n al y
ze
rs a c
t
a s s e
q
u
e nt
i
al
a nd i
nd
e
p
e
nd
e
nt
g
a
t
es
t
h
ro
ug h
w
h i
ch i
o
ns
m
us
t
p
a
ss
t
o
b
e
d
et
e c t e
d
.T
h
e
v
a
l
u eo
f
t
h
e
M
S/
M
S
e xp
e ri m
e
nt
i
s
t
h
a
t
i
t
a
l l
o
w
s
f
o rt
h
e
p
e
rf
o rm
a nc e
of h i g h l y
s e
le c
t
i
v ea
n al y
s e s
.Se
l
e ct
i
vit
y i
nt
h
e
M
S /
M
S
e
xp
e ri m
e
nt
i
s
a ch i
e
ve
d b y p
ro
p
e
rl y
s e
t t
i
ng
t
h
e
f
ir s
t
g
a
t
e
t
o
d
e
fi
n e
t
h
e
i
o
ns e
m
e r
g i
n
g f
ro
m
t
h
e s o
u rc e a n
d
t
h
e s e c o
nd
t
o
d
et
e rm i
n e
t
h
e
m
a s s es o
f
s e c o
nd
a ry i
o
ns
g
e
ne
ra
t
e
d i
nt
h
e
r ea c
t
i
o
n re
g i
o n
b
et w
ee
nt
h
e
t w
oa n a
l y
ze
rs
(
C
o ok
s
,19 83
)
.P
ro
g
e
ny i
o n sf
o r
m
as a
re s
ul
t
of
t
h
e
d i
ss o c
i
a
t
io
no
f
t
h
e
p
a
re
nt
i
o
ns
.T h i
s
d i
s s o c
i
a
t
i
o n
i
s e n
h
a n c e
d
w
h
e n
t
h
e
p
a
re
nt
i
o n s e
nt
e r
a
re a c
t
io n
r
e
g i
o nt
oc o
l l i d
e
w
i
t
h
a
ne u t
ra
l
t
a
rg
e
t
g
as
i
na
p
ro c e s s
ca
l l
e
d
c
ol l i
si
o
ni
nd
uc e
d
d i
s
s oc
ia
t
i
o
n(
C
I
D
)
.T
h
e ab i l i
t
y
t
oe
nh
a
nc
e s el
ec
t
i
vi
t
y h
a s
g
e n e r
at
ed
s
i g
ni fi
c a
nt
re s
ea
rc
h i
nt
e
re s
t
i
nm
ad
e up
of
c om p l
e xm
i
xt
u r e s of
c om
p
o u nd
st
h
at
p
r e s e nt
a n al y
t
i
c al p
r ob
l
em
sw h
e nu s
i
ng l
ow
r e s ol
ut
io n
a nd
h i
g h
r e s ol
ut
i
o nm
a
s s sp
e ct
r om
et
ry
(
H
R
M
S
) (
B
u s ch
,19 8 8
)
.T
h
e u se
of
M
S
/
M
S
as a
r ap i d
s c r e en
in
g t
e
ch
ni q
u ef
o ri d
e nt
i f
i c at
i
o n of 1 14
E P
A p
r
i
o ri
t
y p
o
l l
ut
a nt
s
(p h
e n ol
s
,a
ro
m
at
i
ch y d
ro c a
rb
o ns
,p h
t
h
al
a t e s
,a
nd
c
h l
o r o c a
rb
o
ns
)
w
as
t
h
o r o
ug h l y i
n ve s
t
i g
a
t
e
d b y H
u nt
e
t
a
L
(
19 8 3
)
.T
h
e s e
i
n
ve s
t
i g
a
t
o r s
d
e
m
o
ns t
r at
ed
t
h
ep
ow
e
ro
f
M
S/
M
S
t
o
p
e r
f
o r
m d i
re c
t
s a
m p
l
e a
na
l y
s
i
s
w
i
t
h
o
ut
e x
t
e ns
i
ve s
am p
l
ep
r ep
a r at
io n
or
t
h
e
u se o
f g
as
ch
r om
at
o
g
ra
p h y f
o
rs
ep
a
ra
t
i
o
n .C
om p l
e
xm i
xt
u re s
ra
ng i
ng f
ro
m
c o a
l l i q
ui d
s
t
o
b i
o
l
o
g i
c
al m
a
t
ri
c e s
h
a
ve
b
e e
ns u c c
e s s
f
ul l y
a n al y
z ed b y
th
e us
e of
a
d ir
e c
t
p
r ob
e
i
nt
oa
nM
S/
M
S i
n str u
m
e
nt
(
C
o o
k
s
,19 8 3
)
.D i
re c
t
p
ro
b
e
-
M
S/
M
S
a s a
m
e a
ns
t
o
d
e
t
e
rm in
e
i
s o
m
e r
s
p
e c
i f
ic
i
t
y
w
a s e
xp l
o r e
d
p
ri
o
rt
o
t
h
ed
e v el
op m
e
nt
o
f h i g h
re s o
l
ut
io n
g
as
ch
ro
m
a
t
og
r ap h y
(
H R G C
)
m
et
h
o
d
s
.D i
re
ct
p
r o
b
e a
na
l y
s
i
s
h
as
th
e
l i m i
t
a
t
i
o
nt
h
a
t
i
s o
m
e r
i
n
f
o r
m
a
ti
o
ni
s n o
t
e a s
i l y
a n
d
d i
r e ct
l y
ob
t
ain
a
b l
eb y
t
h i
sm
e
th
o
d
as
w
a s
h
o
p
ed b
e c a us e
m
a
ny i
s om
e
r s of
c om p
o
u nd
s
h
a v ei d
e nt
i
c al f
r ag m
e nt
at
i
o np
at t
e r n s.Si
nc e
i
t
sd
e v elo
p m
e nt
,
h i g h
r e s ol
ut
i
o ng
a s
c
h
ro
m
a
t
o
g
r a
p h y
(
H R G C
)
h
a s
m
a
d
e
i
t
p
o s s
i b l
e
t
o
i d
e n
t
i f y m
o
re
i
s o
m
e r s a n
d
t
h
u s
H
R
G C /
M
S i
s c om m
o nl y
u s ed
t
o a
n al y
ze
vo
l
a t
i l
e c om p
o u
nd
s.T
h
e o
i l i
nd
u st
ry
u se s
G C /
M
S /
M
S
t
o s c
re
e nd
ri l l i
ng
s a
m p l
e s
f
o
rg
e o c
h
e
m i
c a
l b i
o
m
a
rk
e
rs
(
s
t
e
ra
ne s a
nd
t
ri
t
e r
p
a n e s
)
i
ns
it
ua
ti
o
ns
w
h
e
re
b i
o
m
a r
k
e r s a r e
p
re s e n
t
i
n e
xt
r e
m
e
l y l
o
w
c o n c e
nt
r a
t
i
o n s o r
i
n
t
e
rf
e
re
nc e s
f
r o
m
o
th
e
rh y d
r o c a
rb
o
ns
p
re c
l
ud
e
t
h
e
us e o
f G C
/
M
S
(
I
s ak
s e n
,19 9 2
)
.T h
eM
S/
M
S m
et
h
o
d i
s al
s o
us
ed
t
o
i d
e
nt
i f y
e
n vi
r o
nm
e
nt
a
l p
o
l l
ut
a
nt
s
r
a
ng i
ng f
r o
m
t
h
os e
f
o
u nd in
p
ap
e
rm i l l
e
f fl
u
e nt
s
t
o
t
h
o
se
l i
s
t
e
d i
nin
d
oo
r ai
rp
o
l l
ut
i
o n
s
t
ud i
e s(
B
us
ch
,19 8 8
)
, a nd
t
o
a na
l y
z ep
o
l y h
a
l
o
g
e na
t
e
d d i b
e
n z o-p
-d i
d
i
b
e n zo
f
u r a n s(
P
C
D
D /
F
s) (
H
a r v a n ,19 8 1
; R
ei
n e r,1
9 89
,S l
ay b
a c
k 1
9 8 3
; T
o nd
e u r,19 8
7 ;
C h
a
rl
e s,19 9 0
)
.T h
ep
r e s e n c ea
nd f
at
e of
p
ol
y
ch l
ori
n at
ed d i b
e n
z o-/
7-d i
o x
i
n a nd d i b
e n z of
u ra
ns
(
P C
D
D
/
F
s)
i
nt
h
e e n vi
r o nm
e nt
i
s a ni m p
o rt
a nt t
op i
cb
e
c a u s e of
t
h
eh
e al
t
h h
a za
rd
sp
os e
d b y
t
h
e s e
c om
p
o
u nd
sf
o rh
um
a
ns a
nd
o
th
e
rs
p
e c
i
e s
.Sh
o
rt
-
t
e rm h
e a
l
t
h
e
f f
e c
t
s o n
h
um
a ns
e xp
o s ed
t o
re
l
a
t
i
v el
y
h i
g
h l
e v el
s of
P
C
D
D /
F
s
i
n cl
ud
e ch l
o r a c n e,l
i
v e re n
l
a rg
e
m
e
nt
,h
e ad
a c
h
e
s, na
u s ea
,a
nd d
a
m
a
g
e
t
o n e r ve
fi b
e
rs
(
P
ad d
o c
k
,19 8 9
)
.L
o
ng
t
e
rm h
e a
l
th
ef f
e c
t
s
f
r o
m
P
C
D D
/ F
s e
xp
o s
u re a
re s
t
i l l
n o
t
c o
m p l
e
t
e
l y
u nd
e r s
t
o o
d
,b
u
t
t
h
ef
ol
l
ow i
ng h
a v eb
e e nd
et
e rm i
n ed b y
r e s e a r ch
e
rs
a nd d
o c um
e
nt
ed
(
P
a
d d
o
ck
,19 8 9
)
:
2
,3
,7
,8
-
T
C D D
a n
d
o
t
h
e
rP
C
D
D /
F
s a re c a
nc e
rp
ro
m
o
t
e
rs
r at
h
e rth
a ni
ni
ti
at
o r s.B i
rt
h
d
e
f
e ct
sf
r om
e xp
o s
ur e
t
oP
C
D
D /
F
sh
a ve
b
e e
nd
o c um
e n
t
ed i
nc a s
es
w
h
e
re
t
h
e
m
ot
h
e r
w
a s
e xp
o s e
d
t
o
h i g h d
o s e s
w
h i l
ep
re
g
n a
nt
.T h
e
m
u
t
a
g
e
ni
c
i
t
y
o
f 2
,3
,7
,8
-
T C D D i
s
v e r
y
w
e ak
a nd m
o s
t
r e s e a
r ch
e rs
h
a
ve c o
nc
l
ud
e
d
t
h
a
t
i
t
i
s
no
t
a
m
u
t
a
g
e
n .W
h i l
e
d
em
o n st
r at
i
ng h i g h
t
o
xi
c
i
t
y
a nd
c a
rc
i
n og
e ni
c
i
t
y i
n re s e a r c
h
a ni m
al
s
,P
C
D
D /
F
s(p
a r
t
i
c
ul
a r
l y 2
,3
,7
,8
-
T C D D
)
h
a
ve r e c e n
t
l y b
e e n
s
h
o
w
n
t
o
h
a
ve
m
o r e s u
b
t
l
e e
f f
e c
t
s
(
S
ch m i d
t
,19 9 2
)
.I
nc
r e a si
ng
e vi d
e
nc e s
ug g
es
t
st
h
a
t th
e s e c o
m p
o u nd
s'
a
b i l i
t
y
t
o
d i
s r u
p
t
n o
rm
a
l i m m
un e s
y
s
t
e
m f
un c
ti
o
n ra
t
h
e r
t
h
a
nc a r c
i
n o
g
e n
i
c
i
t
y m
a
y
re
p
re s e
nt
t
h
e
i
r
g
re a
t
e s
t th
r e a
t t
o
p
ub l i
c
h
e a
lt
h
(
S
c
h m i d
t
,19 9 2
)
.W
h i l
e
t
h
e s
t
o r
y
o n
h
e a
l
t
h
e
f f
e ct
s
of
P
C D D /
F
s
i
s
st
i l l
u nf
ol d i
ng
,t
h
e c
u rr e
nt t
o
xi
c o
l
o
g i
c a
l i
nf
o
rm
a
ti
o
na
nd
th
e
w
i d
e s
p
re a
d p
re s e
nc e o
f
t
h
e s e
m
a
t
e ri
a
l
s
i
nth
e e n
vi
ro n
m
e n
t
i
n ve
ry l
o
w
c o
nc e
nt
r ati
o n s
h
a s c
re a
t
e
d
th
e
ne e
d f
o
rs e
ns
i
t
i
ve
,s e
l
e c
ti
ve
,a
nd
a c c u r a
t
e
m
a s s s
p
e c
t
ro
m
e
t
ry m
et
h
o
d
s
q
u a nt
i
t
at
i
v et
oo
l
a nd
t h
ea
n al y
si
s
of
P
C
D D
/
F
si
s af
o c u s of
t
h
i
s r e s e a r ch
.M
as s
S p
e c
t
r om
et
ri
cA
n a
l
y
s
i
s of P C D D / F
s
M
a s s sp
e ct
r om
etri
c
a na
l y
si
so
f p
ol y
ch
l
ori
n a t
ed
-d i b
e n z o-/
7-d i
o
xi
n s/ f
u r a ns
(
P C D
D
/ F
s)
h
as
u nd
e
rg
o ne
m
a
ny
r e
fi
ne
m
e nt
s o
ve
rt
he
p
ast
fi f
t
e e
ny
e a r s
(
H
u
a ng
,19 9 1
)
.H i g h
re s o
l
ut
io
nm
a s
ss
p
e c
t
ro
m
e
t
ry
(
H
R
M
S
;
re s
ol
vi
ng p
o
w
e r
10
,0 0 0
o
rg
r e at
e r)
h
a sb
e c om
et
h
em
eth
od
of
ch
oi
c ef
o rP C D
D /
F
a n al
y
si
sf
o rm
o st
l
ab
o r at
ori
es
b
e c
a u se o
f i
t
s
a cc
u ra
cy
a
nd
s e
l
e c
t
i
vit
y
c o
m p
a
re
d
t
o
lo
w
r e s o
l
ut
i
o nm
a
ss s
p
e c
t
ro
m
e
tri
c
m
et
h
od
s
(
H
a
r v a n ,19 8 1
)
.A
na
l y
si
s o
f
P
C D D /
F
s
b y H R
M
S i
s c o n
d
uc
t
e
d
us
i
ng
s
el
e ct
ed i
o
nm
o ni
to
ri
ng
o
r re c o
rd i
ng
(
SI
M
o r
S I R
)
.R
a
th
e
rt
h
a
ns c a n n
i
n
g
t
h
e
f
ul l
m
a s s s
p
e c
t
r um
o
f
t
h
ea
na
l y
t
e o
f i
nt
e r e st
,i
nt
h i
s
m
od
e o nl y
o
n e o rt w
o
o
f
t
h
e
m
o st
i
nt
e
ns
eio
nm
a s s e s a
re
m
o
ni
to
re
d
, re s
ul
t
in
g i
na
10
'
i
nc
re a s e
i
ns e n si
t
i
vi
t
y
o
ve r
f
ul l
s c a n
.T
h
e a
bi l i
t
y
t
o
s u s
ta
i
np
re c
i
s e
m
a s s s e
l
e c
t
io n
i
nh i g h
re s o
l
ut
i
o
nS
I R
i
s
m
a
d
e
p
o s si b l
eb y m
o ni
t
o
ri
ng
a n
i
o
nf
ro
m
t
h
e
m
a s s s
p
e c
t
r
a of
a
re
f
e
re
nc e
c om p
o
u nd
(
e
.g
.lo c
k m
a s s
)
t
h
a
t
i
s c o n
t
i
n u a
l l y i
n
t
r o
d
uc e
d i
n
t
o
t
h
e
i
o n
s o u r c e o
f
t
h
e
i
n s
t
r u
m
e n
t
t
h
ro
ug h
ou
t th
e a n a
l y
s
i
s
.F
o
rP C D D / F
a n a
l y
s
is
,p
e r
fl
o
u ro
ke
ro s e n e
(
PF K
)
i
s u s e
d
a s
t
h
e
r ef
e r e n c e c om
p
o u nd
.A
d i f f
e r e nt
P F
K i
o nm
as
si
sm
o nit
o r ed f
o r e a ch P
C
D
D /
F
c
o ng
e n e rg
ro
up
,a
nd
t
h
e
m
as
s ch
r om
at
og
ra
m
of
t
h
e
P F
K i
o
nm
a s s
i
s
us
ed
t
o ch
e c
k
t
h
e s
t
a
b i l i
t
y
o
f
t
h
e
i
nst
r u
m
e n
t
d
u
ri
n
g S I R
a n a
l y
si
s
.H i g h
r e s o
l
ut
io n
m
a s s
s
p
e c
tr o
m
e
t
r
y
a
na
l y
si
s o
f
e n
vi
r o n
m
e n
t
a
l
s a
m p l
e s
f
o r
P C D D /F
s
do e s
,h
o
w
e
ve r
,h
a
ve
l i m i
t
a
t
i
o n s
.I
nth
e e
n vi
r o nm
e nt
,P C D D / F
s
t
y p i
c
al l y
a
re e
nc o
un
t
e
re
d
at
c o n c e
nt
ra
t
io
nl
e
ve
l
s
(
p
a rt
sp
e rt
ri
l l
i
o n o rq
u ad ri
l l
i
o n)
m
u ch l
ow
e rt
h
a
n oth
e
rt
y p
es
of
e n vi
r o nm
e nt
al
p
ol l
ut
a nt s
(
as
m
uc
h
a s si
x o rd
e r so
f m
ag
ni
t
ud
e)
.P
ol y
c
h l
ori
n at
ed
-
d i b
e n z o
a n
d d i b
e n z of
u r a n sg
e n e r al
l
y
a r ei
n ci
d
e nt
al
b y
-p
r od
u ct
s of i
n ci
n e r at
i
o n o r ch
em
i
c al
r
e a c
t
i
o
ns
a
nd p
r o c e ss e s u s e
d i
nth
e
p
ro
d
uc
t
i
o no
f p
a
p
e r
,w
o o
d
,p
e
st
i
ci d
es
, a nd
P
C B
s
.T h
ep
r e s e n c e of
ot
h
e rm
at
e ri
al
si
nt
h
e s am
p
l
e
c a n af
f
e
ct t
h
em
a s s sp
e ct
r om
et
ri
c
a n a
l y
si
si
nt w
o
w
ay
s
.O
n ep
o s si b i l i
t
y i
s
t
h
a
t
ac
om
p
o u nd
c a n a ct
a s am
a ss
i
nt
e rf
e r a nt
(
i
. e. ,t
h
e c om
p
o u nd h
a st
h
ep
ot
e nt
i
al
t
oi
nt
e rf
e r ew
i
t
h
t h
e a n al
y
si
s of
a n o
t
h
e rw h
e nt
h
ed i f f
e r e n c eb
et
w
e e nt
h
em
a s s e s of
t
h
ei
o n s c a n n ot
s ep
a r at
ed
at a
g i
ve n
re s o
l
vi
n
g p
o
w
e
r(
m /
A
m
)
.A t
a
re s o
l
vi
n
g p
o
w
e
ro
f 10
,
0 0 0 m
a n
y
c o
m m
o n
m
a s s
i
nt
e
rf
e r a nt
s
(
e
.g
.h
e
xa
,
h
e
p
t
a
,o c
t
a
, no
na
P
C
B
s
a nd
t
e
t
ra c
h l
o
ri
na
t
e
d
m
e
t
h
o
xy b i p h
e
ny l
s)
ar e e
l
i m i
n at
e
d
(
T
o
nd
e
u r ,19 87
)
.E l i m i
n ati
o n of
s o
m
em
a s s
i
nt
e rf
e
ra
nt
s c a
n ,h
ow
e
ve r
, r eq
ui
r e re
so
l
vi
ng p
ow
e
ro
f
4
0
,0 0 0
o
rh i g h
e
r(
e
.g
. ,t
h
e
m
ol
e c ul
a ri
o n of h
e xa
-P
C
B
i
nt
e rf
e r e sw
i
t
h
t
h
e(M
-l
-2
)
'^i
o n of
P
eC
D
D
a nd
r eq
ui
re s a
r
e s o
l
vi
ng p
o
w
e ro
f
4
9
,0 0 0
)
.W
h i l
e
c u r r e nt
i
n st
r um
e
nt
at
i
o
ni
s c a
p
a
b l
e o
f h i g h
e
rr
e s o
l
uti
o
n(
5 0
,0 0 0
-10 0
,
0 0
)
,t
h
e s
ub
s e
q
ue n
t
d
e c r e a s e
i
n s e
ns
it
i
vi
t
y
a
t th
e s e
re s o
l
vi
n
g
p
o
w
e
rs
m
a
k
e s s u c
h
a n a
l y
s
i
s
i m p
ra c
t
i
c a
l
.T h
e
i d
e n
ti
t
y
o
f P C D D / F
s
i
s c o
nf i
rm
e
d b y
c o
m p
a r
i
n
g
t
h
e
m
e a s u r e
d
r a
t
i
o s
b
e
t w
e e n
t
w
o
i
o n s
i
n a c
h l
o r
i
n e
i
s o
t
o
p
e r a
ti
o
a n
d
t
h
e
t
h
e o r et
i
c al
v al
u e.T h
ep
r e s e n c eo
f
P
C D D /
F
si
s c o nf
i rm
ed
w h
e nt
h
e
s e r at
i
o s ag
re e
w
i
th i
n
+
15 %
.I t
i
s a s s u
m
e
d
t
h
a
t P
C D D /
F
s a
re a
b
s e
nt
i f
th
e
va
l
ue s e
xc e e
d
th
e s e
l i m i
t
s
.I
t
i
s
p
o s s
i b l
e
,