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VOC's - Jo Dewulf

VOC's - Jo Dewulf

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Solid-phase microextraction of volatile organic compounds
\
Estimation of the sorption equilibrium from the Kovfits index, effect of salinity and humic acids and the study of the kinetics by the development of an "agitated/static layer" model
Solid-phase microextraction of volatile organic compounds
\
Estimation of the sorption equilibrium from the Kovfits index, effect of salinity and humic acids and the study of the kinetics by the development of an "agitated/static layer" model

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E L S E V IE R
Journalof ChromatographyA. 761 (1997) 205-217
JO U R N A L O F
C H R O M A T O G R A P H Y A
S o lid -p h a s e
m ic r o e x tr a c tio n
o f v o la tile
o r g a n ic c o m p o u n d s
E stim ation
o f th e
s o r p tio n
e q u ilib r iu m
f r o m
th e
K o v fits
in d e x ,
effect of salinity
a n d h u m ic
a c id s a n d th e stu d y
o f th e k in e tic s b y
th e d e v e lo p m e n t o f a n
" a g ita te d /s ta tic
la y e r "
m odel
Jo Dewulf, Herm an Van Langenhove*, M aarten Everaert
D e p a r tm e n t o f O r g a n ic C h e m is tr y , F a c u l~
o f A g r ic u ltu r a l a n d A p p lie d B io lo g ic a l S c ie n c e s , U n iv e r s ity o f G h e n t, C o u p u r e L in k s 6 5 3 ,
B -9 0 0 0 G h e n t, B e lg iu m
Received 11 July 1996;revised 25 Septem ber1996;accepted 25 Septem ber1996
A b stract
T h e s o rp tio n e q u ilib riu m a n d k in e tic s o f 11 c h lo rin a te d C ~- a n d C 2 -h y d ro c a rb o n s
and m onocyclic arom atic hydrocarbons
o n th e p o ly (d im e th y ls ilo x a n e ) so lid -p h a se
m ic ro e x tra c tio n
c o a tin g w a s stu d ie d . A lin e a r re g re ssio n b e tw e e n th e lo g a rith m
o f
the partitioning coefficients, corrected
b y H e n r y 's la w
c o n s ta n t, a n d th e K o v fits in d e x e s o n a
1 0 0 % p o ly (d im e th y ls ilo x a n e )
G C
stationary phase
w as show n (r=0.997, n = 11). The effect of salinity in artificial seaw ater on the sorption
e q u ilib riu m
w a s s tu d ie d
a n d c o m p a r e d to th e
salt effect on the
s o lu b ility a n d o n th e a ir - w a te r e q u ilib riu m p a rtitio n in g . T h e e ffe c t o f
h u m ic a c id s
o n
th e
e q u ilib riu m p a rtitio n in g in
SPM E
w as
exam ined and compared
t o
p re d ic tio n s
fro m

m ass balances e s tim a tin g th e im p o rta n c e o f th e m a ss so rb e d o n th e h u m ic a c id fra c tio n . K in e tic s o f th e m a ss tra n s fe r o f th e v o la tile o rg a n ic c o m p o u n d s fro m

the stirred
aqueous phase
in to th e o rg a n ic p h a se
w e re in v e s tig a te d .
Equilibration tim es, i.e., the tim e at
w h ic h
9 5 %
o f
th e
fin a l
s o rb e d
m ass
i s
p re c o n c e n tra te d ,
v a rie d
b e tw e e n
0 .7 7
(1 ,2 -d ic h lo ro e th a n e )
a n d
3 5 .0
m in
(te tra c h lo ro e th y le n e ).
T h e s e e q u ilib ra tio n tim e s w e re lin e a rly re la te d to th e p a rtitio n in g c o e ffic ie n ts ( r = 0 .9 9 3 , n = 11 ). A n e w
m o d e l w a s d e v e lo p e d in o rd e r to s im u la te th e s o rp tio n p ro c e s s . I n th e m o d e l a n a g ita te d

w a te r b o d y a n d a n a q u e o u s s ta tic layer at the w ater-p o ly m er interface w ere considered. It w as assum ed that the m ass transfer w as lim ited by F ickian diffusion in th e a q u e o u s s ta tic la y e r a n d in th e o r g a n ic p h a s e . E x p e r im e n ta l re s u lts c o n firm e d th is a p p ro a c h a n d re v e a le d a s ta tic w a te r la y e r w ith a th ic k n e s s b e tw e e n 3 .0 a n d 5 .5

I~ m fo r b e n z e n e , tric h lo ro e th y le n e
a n d te tra c h lo ro m e th a n e ,
in d ic a tin g th a t th e
a q u e o u s
s ta tic la y e r is d e p e n d e n t o n th e s o rp tio n
equilibrium coefficient.
K eyw ords:
E x tra c tio n
m ethods;
S o rp tio n
e q u ilib riu m ; R e te n tio n in d ic e s ; P a rtitio n
c o e ffic ie n ts ;
K inetic studies; V olatile
organic com pounds; H ydrocarbons; H um ic acids
I .
In tr o d u c tio n
T he
s o lid - p h a s e
m ic ro e x tra c tio n
(S P M E )
p r e c o n -
c e n tra tio n
te c h n iq u e
i s
a
m e th o d
w h ic h
i s
u s e d
t o
p re c o n c e n tra te
v o la tile
o rg a n ic
com pounds
(V O C s)
C o rre sp o n d m g a u th o r.
o u t
o f
a q u e o u s
m atrices
[1 -1 2 ].
A p p lic a tio n s
o f
s o lid - p h a s e
m ic ro e x tra c tio n
fo r
liq u id -(b o u n d e d )
liq u id e x tra c tio n a s w e ll a s fo r th e h e a d s p a c e
[7 ,9 ] is
d e s c rib e d . B rie fly th e
SPM E
a p p a r a tu s
consists of a
p o ly m e r c o a tin g
o n
a
fib e r w h ic h
i s
m o u n te d
o n
a
sy rin g e
n e e d le .
I n
th e
p r o c e d u r e
th e
a n a ly te s
a re
a llo w e d
t o
d iffu se
in to
th e
b o u n d e d
o rg a n ic
p h a s e .
0 0 2 1 -9 6 7 3 /9 7 /$ 1 7 .0 0 C o p y rig h t \u00a9
1 9 9 7 E ls e v ie r S c ie n c e B .V . A ll rig h ts re se rv e d
P II
S 0 0 2 1 -9 6 7 3 (9 6 )0 0 8 1 0 -2
2 0 6
J . D e w u l f e t a l.
/ J. Chromatogr.
A
7 6 1
(1 9 9 7 ) 2 0 5 - 2 1 7
S u b s e q u e n tly
th e y
a r e
th e rm ally
d e s o r b e d
fro m
th e
c o a tin g in a G C
in je c to r. A d v a n ta g e s a re th e a b s e n c e
o f
s o lv e n ts ,
th e
sim p licity ,
th e
lo w
c o s t
a n d
th e
re la tiv e
ra p id ity
o f th e
te c h n iq u e
[ 1 3 ,1 4 ].
Som e
s tu d ie s
re p o rte d
d e a l
w ith
a p p lic a tio n s
o f
SPM E
i n
specific m atrices like
g ro u n d w a te r
[3], air
[6 ,8 ,1 0 ] o r fo o d s [1 5 ]. H o w e v e r, le ss in fo rm a tio n o n
th e
b a s ic
physicochem ical
b a c k g r o u n d
o f
th e
e x -
tra c tio n is p ro v id e d , i.e ., o n th e
s o rp tio n e q u ilib riu m
a n d
k in e tic s
o f
th e
com pounds
in to
th e
o rg a n ic
phase. U sually
e q u ilib ra tio n
tim e s
a r e
a p p ro x im a te d
e m p irically
fro m
a
p lo t o f th e
e x tra c te d
m ass
a s
a
fu n c tio n
o f
th e
e x p o s u r e
tim e
[2 -5 ,1 1 ,1 2 ].
M o d e l-
lin g
o f
th e
p r o c e s s
b a s e d
o n
a
physicochem ical
a p p r o a c h
w as
d o n e
b y
L o u c h
e t
a l.
[4 ]
fo r
d ire c t
liq u id -liq u id
SPM E
e x tra c tio n .
L o u c h e t a l. [4 ] d e v e lo p e d tw o m o d e ls in o rd e r to
d e s c r ib e
th e
s o rp tio n
k in e tic s .
U nder
u n stirre d
c o n -
d itio n s
th e
" u n a g ita te d
m o d e l"
w as
b a s e d
o n
a
F ic k ia n d iffu s io n p ro c e s s b o th in th e w a te r p h a s e a n d
i n
th e
o rg a n ic
p h a s e .
R e s u lts
fro m
th is
a p p r o a c h
fitted the
e x p e rim e n ta l s o rp tio n
profile very w ell. In
p ra c tic e
how ever,
s t i r r i n g
o f
th e
liq u id
i s
th e
p re -
f e r r e d
te c h n iq u e
i n
o rd e r to
a c c e le r a te
th e
p r o c e s s .
Therefore, Louch et al. [4] developed the

" a g ita te d " m o d e l. It w a s b a s e d o n a p e rfe c tly m ix e d w a te r b o d y s o

th a t
th e
p r o c e s s
w as
o n ly
lim ite d
b y
F ic k ia n
d iftu s io n
i n
th e
o rg a n ic
p h a s e .
T h e
e x p e rim e n ta l
e q u ilib ra tio n
tim e s
w ere
s e v e r a l
tim e s
lo n g e r
th a n
th e
th e o re tic a l
v a lu e s
s o
th a t it w a s
c o n c lu d e d
th a t
th e
s o lu tio n
w a s n o t fu lly a g ita te d to e n s u re
th a t th e
sorption process was limited
o n ly b y
m ass transport
th ro u g h
th e
p o ly m e r.
In th e p re s e n t w o rk th e s o rp tio n o f 11 c h lo rin a te d
C 1- and
C 2 - h y d r o c a r b o n s
(C H C s)
a n d

m o n o c y c lic arom atic hydrocarbons (M A H s) out of w ater sam ples o n th e

SPM E
stationary phase
w a s s tu d ie d . E q u ilib -
riu m
p a rtitio n in g
c o e ffic ie n ts w e re d e te rm in e d
and a
re la tio n
w ith the
K o v ~ its in d e x e s w a s e x a m in e d . T h e
e f f e c t
o f
h u m ic
a c id s
a n d
a r t i f i c i a l
s e a
s a lt
w ere
evaluated. The salt effect on SPM E
w a s c o m p a r e d to
th e
salt effect on
s o lu b ility
o f
o rg a n ic
com pounds
a n d
o n
th e
g a s - w a te r e q u ilib riu m
p a rtitio n in g .
N e x t to
th e
e q u ilib riu m
p a rtitio n in g ,
th e
k in e tic s
o f th e
s o rp tio n
o f th e V O C s
o n
th e
SPM E
c o a tin g
w ere
e x a m in e d .
A
m odel
b a s e d
o n
a n

a g ita te d a q u e o u s z o n e a n d a n a q u e o u s s ta tic la y e r, a d ja c e n t to th e

SPM E
p o ly m e r,
w as
d e v e lo p e d
i n
o r d e r
t o
e x p la in
th e
e x p e rim e n ta l re su lts.
2 . E x p e r im e n ta l
T h e
C H C s
c h lo ro fo rm ,
1 ,1 -d ic h lo ro e th a n e ,
1 ,2 -
d ic h lo ro e th a n e ,
1 ,1 ,1 -tric h lo ro e th a n e ,
tric h lo ro -
e th y le n e
( J a n s s e n )
a n d
te tra c h lo ro e th y le n e
(M erck)
a n d
th e
M AHs
b e n z e n e ,
to lu e n e
(M erck),
e th y l-
b e n z e n e
a n d
o -x y le n e
(A ld rich )
w ere
u s e d
i n
th e
e x p e rim e n ts
w ith o u t
a n y
p r e c e d in g

p u rific a tio n . S to c k s o lu tio n s w e re p re p a re d b y in je c tio n o f 5 Ix l o f e a c h

com pound
in to
5
m l
m e th a n o l
(M erck,
fo r
chrom atography, 99.8% ).
In order to calibrate the
SPM E
sam ples a m ixture
o f th e
com pounds
was prepared
i n
d ic h lo ro m e th a n e
(M erck,
fo r
chrom atography,
9 9 .8 % )
a t
c o n c e n tr a -
tio n s o f 1 0 0 ~xl 1- I . K o v fits in d e x e s w e re d e te rm in e d
b y
m e a n s o f a 0 .1 %
s ta n d a r d
of C 5- to C18-alkanes
in C S 2. A w a te r s o lu tio n c o n ta in in g
1 pA m l-1
o f th is
s ta n d a r d
was prepared
fo r e x tra c tio n
b y
SPM E.
A rtificial
s e a
w a te r
w as
p r e p a r e d
fro m
d e io n iz e d
w a te r
a n d
a r t i f i c i a l
s e a
salt (M arine
S e a
S a lt
HW ,
W ie g a n d t, G e r m a n y ) . S o lu tio n s o f 1 .0 % , 3 .5 % , 5 .0 %
a n d
1 0 .0 %
(w /w )
w ere
p r e p a r e d
b y
d is s o lv in g
a n
a p p ro p ria te
am ount
o f
s a lt
i n
2 5 0
m l
d e io n iz e d
water. The
m ain
e le m e n ts
o f th e
salt w ere
c h lo rin e
(5 4 .9 3 % ), s o d iu m
(3 0 .5 3 % ), su lp h a te (7 .6 7 % ), m a g -
n e s iu m
(3 .6 8 % ),
c a lc iu m
(1 .1 8 % )
a n d
p o ta s s iu m
(1 .1 1 % ).
T h e h u m ic a c id s in th e e x p e rim e n ts w e re o b ta in e d
fro m
A ld rich
( H
1 6 7 5 -2 ).
S o lu tio n s
of 20,
1 0 0
a n d
5 0 0
m g
1 -l
were prepared
in d e io n iz e d
w ater.
T h e
SPM E
fib e r c o a te d
w ith
1 0 0
~ m
o f p o ly (d i-
m e th y ls ilo x a n e )
( 1
c m
le n g th )
w as
o b ta in e d
fro m
S u p e lc o . T h e
in n e r d ia m e te r (1 1 0
p~m ) and
th e
f i l m
th ic k n e s s
(1 0 0
p~m ) w ere
m easured
b y
m eans
o f
f lu o r e s c e n c e
m icroscopy.
B e fo re
th e
e x tra c tio n
i t
w as
c o n d itio n e d
at 220\u00b0C
d u rin g
1 0
m in
i n
a
G C
in je c to r.
T h e
SPM E
o rg a n ic
p h a s e
w as
e x p o s e d
t o
a q u e o u s
s o lu tio n s
(3 8 .7
m l)
i n
4 0
m l
c y lin d ric a l
v ia ls
(in n e r d ia m e te r 2 .5
cm ), sealed
b y
s c r e w
c a p s
w ith
P T F E /s ilic o n e
s e p ta
(S u p e lc o ).
T h e
s o lu tio n s
w ere
s t i r r e d
b y
a
m a g n e tic
s t i r r i n g
b a r
a n d
a
m a g n e tic
s t i r r e r
(IK A -C o m b im ag
R E T ,
J a n k e
a n d
K u n k e l) a t 7 0 0
rp m .
T h e
G C
analyses of the V O Cs preconcentrated on
th e
SPM E
s ta tio n a ry
p h a s e ,
w ere
c a rrie d
o u t
o n
a
V arian
g a s
chrom atograph
M odel
3 7 0 0 ,
e q u ip p e d
w ith
a
flam e
io n iz a tio n
d e te c to r
a n d
a
H P
3 3 8 8 A
in te g ra to r.
In je c to r
te m p e ra tu re
a n d
d e te c to r
tem -
p e ra tu re
w ere
1 6 0 \u00b0 C
a n d
220\u00b0C ,
re s p e c tiv e ly .
T h e
J .
D ew ulf et al.
/
J .
C hrom atogr.
A
7 6 1
(1 9 9 7 )
2 0 .';-2 1 7
2 0 7
c a rrie r g a s w a s h e liu m
(flow -rate 4.3 m l m in-l, inlet
p r e s s u r e
i03 kPa). The detector w as fed by air at 285
m l
r a in
~
a n d
H 2-gas
a t
3 3 .8
m l
m in -~
T he
com pounds w ere separated on a 30 m \u00d70.53
m m
I.D .
D B -1
c a p illa ry
c o lu m n
( f i l m
th ic k n e s s 5
Ix m , J a n d
W
S c ie n tific ).
D u rin g
th e a n a ly s is th e G C
oven was
kept at 40\u00b0C
d u rin g 5 m in a n d h e a te d u p to
150\u00b0C at
a rate of 5\u00b0C
m in
~. Kov~its indexes were m easured
at 60\u00b0C
(in je c to r te m p e ra tu re
220\u00b0C ).
L iq u id
s o lu tio n s
w ere
a n a ly s e d
o n
th e
sam e
G C
system . V olum es o f 1 txl w ere injected at 220\u00b0C . T he
G C
oven tem perature w as kept at 24\u00b0C
(by m eans of
liq u id
n itro g e n ) d u rin g
1 7
r a i n
a n d
th e
te m p e ra tu re
w as raised
at a rate
of 4\u00b0C
m in -J
up to
1 4 0 \u00b0 C
a n d
h e ld
for 2 m in
a t th is te m p e ra tu re .
I n
o rd e r
t o
sim u late
th e
s o rp tio n
k in e tic s
o f th e
V O C s
o n
th e
SPM E
p o ly m e r
a
M icrosoft
F O R -
T R A N
O p tim iz in g
C o m p ile r
(v e rsio n
5 .0 0 )
w as
u s e d .
T a b le
1
E x p e rim e n ta l K
v a lu e s , re la tiv e d e v ia tio n s o n
K
in %
(R .S .D .% )
(n = 3 ),
K o v ~ its
re te n tio n
in d e x e s
(lk )
(n -2 )
a n d
H e n r y 's
la w
constant (H )
V O C
K
( - )
R .S .D .%
I ~
H ~'
o n
K
C h lo ro fo rm
3 3 _+ I
3 .7
6 0 5 .5 _ + 1 .2
0 .1 1 9
T e tra c h lo ro m e th a n e
3 4 2 + _ 2 2
6 .5
6 5 9 .7 + 1 .3
0 .8 3 6
1 ,1 - D i c h l o r o e t h a n e
3 3 + _ 1
4 .1
5 6 0 .4 _ + 1 .4
0 .1 5 8
1 ,2 -D ic h lo ro e th a n e
1 2 -+ 1
5 .8
6 3 0 .2 _ + 1 .4
0 .0 3 3 4
l,l,l-T ric h lo ro e th a n e
2 0 7 _ + 1 2
5 .5
6 3 8 .9 _ + 1 .3
0 .4 8 0
T ric h lo ro e th y le n e
166_+ 11
6 .2
6 9 1 .3 _ + 1 .2
0 .2 6 5
T e tra c h lo ro e th y le n e
8 4 1 _ + 5 9
9 .4
8 0 3 .3 _ + 1 .2
0 .4 5 0
B enzene
7 3 _ + 3
4 .3
6 5 4 .5 _
+ 1.3
0 .1 5 8
T o lu e n e
2 2 5 _ + 1 2
5 .2
7 5 8 .1 + 1 .2
0 .1 7 9
E th y lb e n z e n e
6 5 9 _ + 4 1
7 .5
8 5 0 .1 _ + 1 .3
0 .2 0 5
o -X y le n e
5 4 3 + _ 3 6
7 .3
8 8 0 .2 + _ 1 .2
0 .1 3 0
T h e
s ta n d a rd d e v ia tio n s o n
K
v a lu e s a re
c a lc u la te d
a c c o r d in g
t o
Eq. (3).
H
(dim ensionless) calculated from
ln (H )-a .T
~+b, where T is
th e a b s o lu te te m p e ra tu re
(2 9 3
K) and a
and b
a re o b ta in e d
fro m
Ref. [17].
3 .
R esu lts
a n d
d iscu ssio n
3 .1 .
S o r p tio n
e q u ilib r iu m
o f th e
V O C s on
th e
SPM E
p o ly m e r
3 .1 . I.
E x p e r im e n ta l
r e s u lts
T he
p a rtitio n in g
c o e ffic ie n t
K
o f
1 1
V O C s
b e -
tw e e n th e S P M E
p o ly m e r a n d (d e io n iz e d ) w a te r w a s
d e te rm in e d
a fte r
a
4 5
r a i n
e x tra c tio n
tim e .
T he
p a rtitio n in g
c o e ffic ie n t K
w a s c a lc u la te d
fro m
R A
K -
(1 )
V C w
w h e re
K
is the
SPM E
o rg a n ic p h a s e - w a te r e q u ilib -
riu m
p a rtitio n in g
c o e ffic ie n t (d im e n s io n le s s ), C w th e
c o n c e n tra tio n
i n
th e
w a te r
p h a s e
(n g
m l
~), A
th e
n u m b e r o f a re a u n its o f th e V O C
in the G C
a n a ly s is
o f
th e
SPM E
c o a tin g
(a re a
u n it),
R
th e
r e s p o n s e
fa c to r
fo r
th e
V O C
o f
th e
G C -d e te c to r
[n g (a re a
u n it) -1 ]
a n d
V
th e
v o lu m e
o f
th e
SPM E
o rg a n ic
p h a s e (0 .0 0 0 6 6 m l). T h e re s u lts a re g iv e n in T a b le
I .
T he
a q u e o u s c o n c e n tra tio n s o f th e V O C s a t e q u ilib -
riu m
w ere
assum ed
t o
b e
e q u a l
t o
th e
in itia l
c o n -
c e n tra tio n s b e c a u s e
it w a s p ro v e n b y th e c a lc u la tio n
o f th e
m ass
b a la n c e
th a t th e
a q u e o u s

c o n c e n tra tio n d o n o t c h a n g e s u b s ta n tia lly b y th e fra c tio n s o rb e d o n th e

s ta tio n a ry
p h a s e
[e q u ilib riu m
c o n c e n tra tio n s b e -
tw e e n
9 8 .6 %
(te tra c h lo ro e th y le n e )
a n d
9 9 .8 %
(1 ,2 -
d ic h lo ro e th a n e ) o f th e
in itia l
c o n c e n tra tio n , d e p e n d -
in g
o n
K ].
T he
v a r ia n c e
o n
th e
e x p e rim e n ta lly
d e te rm in e d
v a lu e fo r K
is d e p e n d e n t o n th e v a r ia n c e s o n R , A , V
a n d
C w :
ere(K )
=
\ OR /
"\u00b0 '2 ( R ) + \ ~ - !
' cr2 (A )
+ \O V /
" \u00b0'2 (V )+ \~ C w J
o --(C ~ )
(2 )
T he
c o n trib u tio n s to
th e
v a r ia n c e
o f th e
p r e p a r a -
tio n
o f th e
a q u e o u s
s o lu tio n
(C w ) (relativ e
s ta n d a r d
d e v ia tio n
- - - - -1% )can
b e
n e g le c te d
i n
com parison
t o
th e c o n trib u tio n to th e v a ria n c e o f th e g a s c h ro m a to -
g ra p h ic
d e te rm in a tio n
[re la tiv e
s ta n d a r d
d e v ia tio n
b e tw e e n
1 .5 a n d 5 .7 %
fo r R (n = 5 )
a n d b e tw e e n
5 .0
a n d
8 .3 %
for A
(n = 3 ).
A nd since V
is c o n s ta n t, th e
la tte r e q u a tio n
can be
w ritte n
a s
= \3 R /
" \u00b0 '2 ( R ) +
~
" \u00b0 '2 ( A )
(3 )
F ro m
th e d a ta o n
o r(R ) a n d o n

~ r(A ) to g e th e r w ith th e c a lc u la tio n o f th e p a rtia l d e riv a tiv e s , th e s ta n d a rd d e v ia tio n s

o n
K
a re
c a lc u la te d
a n d
p r e s e n te d
i n
T a b le
1 .
In the literature,
K
values are found for the CH Cs

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