Analytical method development using functionalized polysulfone membranes for the determination of chlorinated hydrocarbons in water.

Abstract

In this study, functionalized polysulfone membrane has been utilized as a sorbent for the extraction of chlorinated hydrocarbons (CHCs) in water samples. Two different functionalized polysulfones (i) phosphonic acid functionalized polysulfone (PPSU-A) with different forms (cross-linked and non cross-linked) membranes and (ii) phosphonic ester functionalized polysulfone (PPSU-E) with different forms (cross-linked and non cross-linked) were evaluated for the extraction of CHCs in water. A 10 ml of spiked water sample was extracted with 50mg piece of the functionalized membrane. After extraction, the membrane was desorbed by organic solvent and the extract was analyzed by gas chromatography-mass spectrometry. Eight CHCs, 1,3,5-trichlorobenzene (1,3,5-TCB), 1,2,3-trichlorobenzene (1,2,3-TCB), 1,1,2,3,4,4-hexachloro-1,3-butadiene (HCBD), 1,2,4-trichloro-3-methylbenzene (TCMB), 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB), pentachlorobenzene (PeCB) and hexachlorobenzene (HCB) were used as model compounds. Experimental parameters such as extraction time, desorption time, types of polymer membrane as well the nature of desorption solvent were optimized. Using optimum extraction conditions calibration curves were linear with coefficients of determination between 0.9954 and 0.9999 over wide range of concentrations (0.05-100 μgl(-1)). The method detection limits (at a signal-to-noise ratio of 3) were in the range of 0.4-3.9 ng l(-1). The proposed method was evaluated for the determination of CHCs in drinking water samples.

Full text

Page 1

Talanta
87 (2011) 284–
289
Contents
lists
available
at SciVerse
ScienceDirect
Talanta
jo u r n al
hom
epage:
www.elsevier.com/locate/talanta
Analytical
the
method
development
using
functionalized
polysulfone
membranes
for
determination
of
chlorinated
hydrocarbons
in
water
Abdulmumin
Abdul
A.
Nuhua,
Chanbasha
Basheera,∗,
Nedal
Y.
Abu-Thabitb,
Khalid
Alhooshania,b,
Rahman
Al-Arfaja
aDepartment
bCenter
of Chemistry,
King
Fahd
University
of
Petroleum
and
Minerals,
KFUPM
Box
1509,
Dhahran
31261,
Saudi
Arabia
of
Research
Excellence
in Nanotechnology,
King
Fahd
University
of
Petroleum
and
Minerals,
Dhahran
31261,
Saudi
Arabia
a
r
t
i
c
l
e

i
n
f
o
Article
Received
Received
Accepted
Available online 19 October 2011
history:
11 July
2011
in revised
form
4 October
2011
13 October
2011
Keywords:
Microextraction
Functionalized
Phosphonated
Environmental
Gas
membrane
polysulfone
analysis
chromatography–mass
spectrometry
a
b
s
t
r
a
c
t
In
extraction
polysulfones
linked
(PPSU-E)
tion
the
and
trichlorobenzene
(HCBD),
tetrachlorobenzene
as
mer
conditions
over
ratio
of
this
study,
functionalized
polysulfone
membrane
has
been
utilized
as
a
sorbent
for
the
of
chlorinated
hydrocarbons
(CHCs)
in
water
samples.
Two
different
functionalized
(i)
phosphonic
acid
functionalized
polysulfone
(PPSU-A)
with
different
forms
(cross-
and
non
cross-linked)
membranes
and
(ii)
phosphonic
ester
functionalized
polysulfone
with
different
forms
(cross-linked
and
non
cross-linked)
were
evaluated
for
the
extrac-
of
CHCs
in
water. A
10
ml
of
spiked
water
sample
was
extracted
with
50
mg
piece
of
functionalized
membrane.
After
extraction,
the
membrane
was
desorbed
by
organic
solvent
the
extract
was
analyzed
by
gas
chromatography–mass
spectrometry.
Eight
CHCs,
1,3,5-
(1,3,5-TCB),
1,2,3-trichlorobenzene
(1,2,3-TCB),
1,1,2,3,4,4-hexachloro-1,3-butadiene
1,2,4-trichloro-3-methylbenzene
(TCMB),
1,2,3,4-tetrachlorobenzene
(1,2,3,4-TeCB),
1,2,4,5-
(1,2,4,5-TeCB),
pentachlorobenzene
(PeCB)
and
hexachlorobenzene
(HCB)
were
used
model
compounds.
Experimental
parameters
such
as
extraction
time,
desorption
time,
types
of
poly-
membrane
as
well
the
nature
of
desorption
solvent
were
optimized.
Using
optimum
extraction
calibration
curves
were
linear
with
coefficients
of
determination
between
0.9954
and
0.9999
wide
range
of
concentrations
(0.05–100
?g
l−1).
The
method
detection
limits
(at
a
signal-to-noise
of
3)
were
in
the
range
of
0.4–3.9
ng
l−1. The
proposed
method
was
evaluated
for
the
determination
CHCs
in
drinking
water
samples.
© 2011 Elsevier B.V. All rights reserved.
1.
Introduction
Chlorinated
a variety
chlorobenzenes,
tain
Beginning
have
mainly
also
deodorants,
Anthropogenically,
a
waste
air,
sediments
hydrocarbons
(CHCs)
or organochlorines
are
of
volatile
and
semi-volatile
compounds
including
chloroethanes,
and
chlorotoluenes
which
con-
at least
one
chlorine
atom
covalently
bonded
to a carbon.
from
the
early
1940s,
many
compounds
of
this
nature
been
designed
for
various
reasons,
the
initial
one
being
the
exploitation
of
their
insecticidal
potentials.
CHCs
have
been
widely
employed
as
solvents,
heat
transfer
agents,
degreasers
and
intermediates
in dye
production
[1,2].
these
compounds
enter
the
environment
as
result
of
emissions,
industrial
effluents,
and
via
inefficient
disposals
[3].
Consequently,
they
can
now
be
found
in the
food,
soil,
surface,
ground,
and
drinking
water
systems
and
[4,5]. Many
marine
organisms
can
also
harbor
these
∗Corresponding
E-mail
author.
Tel.:
+966
3860
7344;
fax:
+966
3860
4277.
address:
cbasheer@kfupm.edu.sa
(C.
Basheer).
pollutants
mon
women
isolated
locations
rine
at
were
[11].
Though
cells,
dichlorodiphenyltrichloroethane
Toxicity
edema,
CHCs
may
[14].
Many
chemical
persistence
health
[6].
Recently,
CHCs
were
detected
in high
arctic
com-
eiders
[7],
and
in the
breast
adipose
tissue
of
California
undergoing
biopsy
[8].
Different
kinds
of
CHCs
were
also
from
breast
milk
of
residents
of
Hong
Kong
and
other
in China
[9,10].
The
daily
dietary
intake
of organochlo-
pesticides
in the
Danish
population
has
been
estimated
between
0.03
and
0.3
?g/day.
Fish,
meat
and
dairy
products
recognized
as
the
major
contributors
to these
estimates
some
types
of
CHCs
are
natural
components
of
human
bacteria
and
lichens,
many
others
including
the
infamous
(DDT)
are
well
known
toxins.
can
be
elicited
in the
form
of
pericardial
and
yolk
sac
cardiovascular
dysfunction,
and
skeletal
deformities
[12].
can
also
interfere
with
drug
metabolism
in the
body
[13], and
cause
reproductive
effects
including
spontaneous
abortions
types
of
these
compounds
can
resist
degradation
by
or
biological
means,
giving
rise
to their
environmental
[15]. Hence,
CHCs
are
increasingly
becoming
a major
concern,
and
this
calls
for
correct
and
sensitive
means
of
0039-9140/$
doi:10.1016/j.talanta.2011.10.019
– see
front
matter ©

2011 Elsevier B.V. All rights reserved.

Page 2

A.A.
Nuhu
et al.
/ Talanta
87 (2011) 284–
289
285
their
in
component
of
ionization
for
trometric
of
CHCs
therefore,
ally
such
tion
often
usually
To reduce
ries,
analytes
simpler
ronmentally
methods
different
tion
in the
Different
ery
suitable
method
less
polymeric
[22].
tive
are
stitute
diverse
porous
from
mer
monitoring
The
brane
via
of
high
hydrophilic
polar
branes
membranes
branes
for
bacteria
carbons
[31]
nic
compounds
nic
Hence,
ized
of
Recently,
phonic
chloromethylation
utilizing
in
the
acid.
determination.
Gas
chromatography
(GC)
is widely
utilized
the
quantitative
determination
of
CHCs.
After
separation,
the
analytes
can
be
detected
by means
of different
types
detectors.
Both
electron
capture
detector
(ECD)
[16]
and
flame
detector
(FID)
[17]
can
offer
low
limits
of detection
(LOD)
trace
amounts
of
CHCs.
However,
GC
coupled
with
mass
spec-
detection
may
provide
for
even
better
resolution
and
ease
identification
of
peaks
[18].
are
present
at trace
levels
in the
environmental
samples,
extraction
and
pre-concentration
procedures
are
usu-
employed
before
the
quantitative
analysis.
Traditional
methods
as
liquid–liquid
extraction
(LLE)
and
solid
phase
extrac-
(SPE)
can
be used
[19], but
they
are
time
consuming
and
involve
the
use
of
large
sample
or solvent
volumes.
These
multi-step
procedures
can
also
lead
to loss
of
analytes.
the
volume
of
waste
solvents
generated
in laborato-
and
to expedite
analysis,
alternative
sample
preps
for
these
are
needed.
This
quest
has
led
to the
development
of
sample
preparation
techniques
that
are
also
more
envi-
friendly.
In the
last
decade
or so,
many
promising
that
can
be
suitable
for
the
extraction
of
CHCs
from
media
have
been
developed.
A liquid-phase
microextrac-
(LPME)
which
minimizes
solvent
use
has
found
applications
analysis
of
pesticides
including
those
of
CHCs
origin
[20].
solvents
are
often
tested
for
optimum
extraction
recov-
and
a mixture
of
chloroform
and
methanol
has
been
found
for
the
extraction
of
these
compounds
[21]. A different
which
extracts
analytes
based
on
sorption
is the
solvent-
technique
called
solid
phase
microextraction
(SPME);
it uses
coating
on
fibers
to extract
and
pre-concentrate
analytes
However,
SPME
fibers
are
expensive
and
have
limited
sorp-
phase
[23]. To overcome
these
limitations,
many
researchers
now
experimenting
with
various
types
of
materials
as
sub-
sorbents
for
application
in the
extraction
of
analytes
of
polarities.
Lu et
al.
[24]
have
employed
chitosan
beads
and
crab
shell
as
sorbents
for
the
removal
of
seventeen
CHCs
water.
Recently,
we
have
introduced
a functionalized
poly-
coated
microextraction
technique
for
routine
environmental
[25].
selectivity
and
sorption
ability
of
certain
sorptive
mem-
is usually
improved
through
attachment
of
functional
groups
chemical
reactions
[26]. For
example,
the
hydrophobic
nature
neat
polysulfone
(PSU),
an
engineering
polymer
possessing
thermal
and
mechanical
stability,
can
be changed
into
more
one
by grafting
the
PSU
backbone
with
a
variety
of
functional
groups
that
generate
various
functionalized
mem-
suitable
for
different
applications,
such
as
polyelectrolyte
for
fuel
cell
applications
[27], nanofiltration
mem-
with
enhanced
antifouling
properties
[28], sorbing
carrier
isolation
of
adherent
polyaromatic
hydrocarbons
degrading
[29]
or as
a membrane
for
separation
of certain
hydro-
such
as
olefins
and
paraffins
[30]. The
use
of
polyimide
and
polystyrene
[32]
that
were
functionalized
with
phospho-
ester
groups
has
resulted
in improved
separation
of
aromatic
(? electron
donors)
due
to the
high
affinity
of phospho-
ester
groups
(? electron
acceptors)
toward
these
compounds.
it can
be
suggested
that
phosphonic
acid/ester
functional-
polymers
can
be
used
as
candidates
for
extraction
and
removal
aromatic
chlorinated
hydrocarbons
from
water
samples.
phosphonated
PSUs
were
introduced
with
high
phos-
acid
functionality
to the
PSU
by
two
steps
procedure,
of
PSU
backbone
followed
by phosphonation
Michaels–Arbuzov
reaction
[33]. Then
phosphonated
PSU
their
ester
forms
(PPSU-E)
were
quantitatively
hydrolyzed
into
corresponding
acid
forms
(PPSU-A)
by
refluxing
in hydrochloric
In
the
present
study,
we
introduced
the
first
example
of utiliz-
ing
sorption
from
phosphonated
PSU
membranes
in their
acid
and
ester
forms
as
matrices
for
micro
solid-phase
extraction
(?-SPE)
of
CHCs
water.
2.
Materials
and
methods
2.1.
Reagents
and
materials
Spectrometric
acetone
ical
used
Sigma–Aldrich
were
buffer
(BDH
lab
prepared
was
chased
was
Nanopure
tem.
Four
as
membranes
tains
includes
have
the
performance.
These
number
chlorinated,
exception
aromatic.
grade
xylene
(Fluka
Chemie
AG,
Switzerland),
(Lab-Scan
Analytical
Sciences),
n-hexane
(J.T.
Baker
Chem-
Co,
USA),
and
toluene
(HiperSolv,
BDH,
Australia)
were
in this
study.
Methanol
(HPLC-grade)
was
purchased
from
(St.
Louis,
MO).
Certified
alkaline
buffer
solutions
supplied
by
Fischer
Chemical
Ltd
(St.
Louis,
MO).
Acidic
solutions
were
prepared
from
anhydrous
sodium
acetate
Chemicals
Ltd,
VWR,
USA)
and
glacial
acetic
acid
(Win-
Ltd,
Leicestershire,
UK).
Sodium
hydroxide
(NaOH)
solution
from
NaOH
pellets
(Riedel-de-Haen,
AG,
Switzerland)
used
for
pH adjustment.
CHC
mixed
standards
were
pur-
from
Supelco
(Bellefonte,
PA).
10
?g ml−1working
standard
prepared
in acetone.
Ultra
pure
water
was
prepared
using
water
purification
(Barnstead,
Dubuque,
IA,
USA)
sys-
different
membranes
were
considered
for
investigation
potential
polymeric
matrices
for
the
extraction
of
CHCs.
These
can
be
categorized
into
two
groups;
the
first
group
con-
the
phosphonic
acid
functionalized
PSU
and
the
second
group
the
phosphonic
ester
functionalized
ones.
Both
groups
one
cross-linked
PSU
and
a non-cross-linked
one,
to enable
evaluation
of
the
effect
of
crosslinking
on
membrane/polymer
analytes
can
be
classified
into
four
groups
based
on the
of chlorine
atoms
in their
structures:
trichlorinated,
tetra-
pentachlorinated
and
hexachlorinated
CHCs.
With
the
of
HCBD,
which
is a conjugated
alkene,
all
other
CHCs
are
2.2.
Instrumentation
The
eight
CHCs
were
separated
on
gas
chromatography-mass
spectrometric
autosampler
through
libraries.
sions
phase
was
50◦C,
held
ture
until
interface
Ion
550
mode
TCMB,
182,
(GC–MS)
6890N
system
(Agilent)
equipped
with
7683B
series
and
a 6890B
injector.
It was
operated
a Chemstation
which
contained
an NIST
98.L
and
wiley7n.l
An
Agilent
19091Z-213
column
of
30 m × 0.32
mm
dimen-
and
a film
thickness
of 1 ?m
HP-1
methyl
siloxane
stationary
were
used.
High
purity
helium
flowing
at
a
rate
of 2 ml
min−1
the
carrier
gas.
The
column
temperature
was
initially
set
at
and
then
increased
to 250◦C at
the
rate
of
10◦C min−1. It was
at the
250◦C for
2 min
and
then
ramped
to the
final
tempera-
of
300◦C at
a linear
rate
of
20◦C min−1. This
was
maintained
the
end
of
the
run
time
of 25.50
min.
The
injector
(splitless),
and
detector
temperatures
were
all
set
at 250◦C.
Total
Current
(TIC)
in SCAN
mode
for
ions
of masses
between
50 and
was
used
for
acquisition,
and
Selective
Ion
Monitoring
(SIM)
was
used
for
quantification
of
1,3,5-TCB,
1,2,3-TCB,
HCBD,
1,2,3,4-TeCB,
1,2,4,5-TeCB,
PeCB
and
HCB
with
m/z
of
180,
260,
194,
216,
214,
250
and
284,
respectively.
2.3.
Water
sample
collection
Three
brands
of
bottled
water,
all
produced
in
Saudi
Arabia,
were
used;
source
purchased
glass
NOVA,
with
source
from
Nuffoud
Al-Wasse’e,
SHIFA
with
in Al-Hasa
and
AFNAN
with
source
in Riyadh.
They
were
from
a local
store.
Tap
water
samples
were
collected
in
bottles
from
Riyadh,
Khafji
and
Rastanura,
different
locations

Page 3

286
A.A.
Nuhu
et
al.
/ Talanta
87 (2011) 284–
289
in Saudi
before
any
Arabia.
They
were
wrapped
with
paper
and
stored
at 4◦C
use.
All
the
samples
were
extracted
in the
laboratory
without
pretreatment
performed.
2.4.
Extraction
with
functionalized
PSU
membranes
All
extractions
were
performed
in the
laboratory
according
to
the
30-ml
piece
was
brane
water.
addition
were
was
the
sonicated
blank
membrane
be
mance.
following
procedure:
10 ml
ultrapure
water
was
placed
in a
vial
and
spiked
with
20
?g l−1of CHC
mixture
and
50 mg
of
the
functionalized
membrane
was
placed.
The
sample
vial
agitated
at 1200
rpm.
After
extraction
for
50 min,
the
mem-
was
removed
and
dabbed
dry
with
lint-free
tissue
to remove
The
membrane
was
then
placed
in a vial,
followed
by
the
of 200
?l methanol
for
solvent
desorption.
The
analytes
desorbed
via
ultrasonication
for
5 min.
Finally,
2 ?l of
extract
injected
in to the
GC–MS
for
analysis.
After
each
extraction,
membrane
was
cleaned
and
conditioned
with
acetone
(ultra-
for
10 min)
to avoid
any
carry
over.
After
conditioning,
extraction
performed
and
no carryover
was
observed,
the
was
reused
after
each
extraction.
The
membrane
could
re-used
for
at
least
ten
times
without
compromising
its
perfor-
3.
Results
and
discussion
3.1.
Effect
of
extraction
and
desorption
times
Extraction
was
performed
at different
times
between
10
and
50
lyte
this
require
extraction.
tion,
agitation
solvent
from
the
desorption,
observed.
sample
subsequent
min.
As
an
index
of
extraction
efficacy,
the
peak
area
of
ana-
was
observed
after
each
extraction
time
considered.
Within
range,
50
min
appeared
to be
the
best
time.
It would
probably
much
longer
time
for
all
the
analytes
to attain
optimum
Therefore,
to avoid
excessively
long
experiment
dura-
all
further
experiments
were
performed
using
50 min
as
the
(extraction)
time.
Similarly,
analytes
were
desorbed
in
via
ultrasonication
and
desorption
duration
was
studied
5 to 20 min.
Generally,
5 min
appeared
to be
suitable
for
ultrasonic
desorption
of
most
the
analytes.
However,
>5
min
there
is
no
additional
increments
in peak
areas
were
This
short
desorption
time
contributes
to the
speed
of
preparation
step
and
was,
therefore,
selected
for
use
in
experiments.
3.2.
Effect
of
polymeric
matrix
The
interaction
of
the
eight
analytes
with
the
two
groups
of
phosphonated
For
in
case
be
of
bonding
higher
compared
ability
the
the
pH
by
ally,
sorbed
membranes
these
PSU
was
investigated
as
shown
in Fig.
1.
all
the
CHCs,
it was
found
that
the
response
was
much
higher
the
case
of
phosphonic
acid
functionalized
PSU
(PPSU-As)
than
in
of
phosphonic
ester
functionalized
PSU
(PPSU-Es).
This
might
attributed
to the
enhanced
? electron
acceptor
property
in case
presence
of
acid
functionality
which
can
form
a
type
of hydrogen
with
the
?
electron
donor
aromatic
rings.
In addition,
the
hydrophilicity
of
the
phosphonic
acid
functionalized
PSUs
to their
ester
counterparts,
can
allow
better
extraction
of
the
hydrophilic
CHC
analytes
as
might
be
inferred
from
selection
of
polar
desorption
solvent
(vide
infra).
Fig.
1 shows
peak
areas
obtained
for
the
analytes
after
50 min
extraction
at
7 using
different
functionalized
materials
as
sorbents
followed
desorption
in xylene
for
5 min.
This
result
indicates
that,
gener-
the
conjugated
hexachlorinated
1,3-butadiene
was
much
less
compared
to the
aromatic
ones,
and
the
non-cross-linked
were
better
sorbents
than
the
cross-linked
ones
under
experimental
conditions.
Therefore,
PPSU-A
0.75
which
Fig.
of
tion
140%
ester
1.
Effect
of
phosphonated
polysulfone
polymer/membrane
types
on peak
areas
CHCs
using
xylene
as solvent,
at experimental
conditions
of
pH 7,
50 min
extrac-
and
5 min
desorption.
0.75,
1.4
and
2.0
in the
sorbent
names
correspond
to 75%,
and
200%
degrees
of
phosphonation,
respectively;
‘A’
and
‘E’
stand
for
acid
and
functionalities
while
‘C’
indicates
the
presence
of
cross-links.
Fig.
pH
2.
Effect
of
solvent
types
on
peak
areas
of
CHCs
at experimental
conditions
of
7,
50
min
extraction,
and
5 min
desorption,
with
PPSU-A
0.75
as
sorbent.
displayed
as
the
best
response
for
most
of
the
analytes
was
selected
the
sorbent
material
in subsequent
experiments.
3.3.
Choice
of desorption
solvent
In
order
to have
better
extraction
efficiency,
different
solvents
were
tested
All
Non
ability
tionalized
the
observation
as
However,
water
of
to
solvents.
gen
as
the
as
shown
in Fig.
2.
membranes/polymers
were
insoluble
in the
tested
solvents.
polar
solvents
like
hexane,
toluene
and
xylene
showed
weak
to desorb
the
analytes
from
the
phosphonic
acid
func-
membranes/polymers
due
to the
large
difference
in
hydrophilic
character
of
the
solvent-polymer
system.
Similar
was
found
in the
case
of using
long
chain
alcohol
such
1-octanol.
methanol
which
has
a similar
geometric
structure
to
was
found
to provide
the
best
interaction
and
desorption
the
analytes
from
the
functionalized
membranes/polymers
due
its
higher
hydrophilic
and
polar
characters
compared
to other
In addition,
methanol
can
have
interaction
through
hydro-
bonding
[34]
with
phosphonic
acid
functionalized
PSUs
as
well
the
chlorinated
benzenes
which
make
it possible
to pull
out
organic
chlorinated
hydrocarbons
from
the
polymeric
matrix.

Page 4

A.A.
Nuhu
et al.
/ Talanta
87 (2011) 284–
289
287
Table
Calibration
1
parameters,
LODs
and
LOQs
for
the
chlorinated
hydrocarbons.
Analytes

Slope
± SDa(×10−5)
2.25
2.07 ±
1.02
2.55
10.00
4.09
2.53
3.21
Intercept
± SD (×10−4)
r2 b
LODc(ng
l−1)
LOQd(ng
l−1)
1,3,5-TCB
1,2,3-TCB
HCBD
TCMB
1,2,3,4-TeCB
1,2,4,5-TeCB
PeCB
HCB
± 0.098

5.67
8.07 ±
0.55
−0.18
4.46
66.19
1.85
−0.47
± 0.694

0.9998
0.9975
0.9997
0.9995
0.9981
0.9954
0.9998
0.9999

1.8
1.9
3.9
1.6
0.4
1.0
1.6
1.3
6.0
6.3
13.0
5.3
1.3
3.3
5.3
4.3
0.023
1.062

± 0.004
± 0.327

± 0.021
± 0.329

± 0.077
± 15.862

± 0.025
± 6.069

± 0.015
± 1.948

± 0.030
± 0.769

aSD,
bCoefficient
cEstimated
dEstimated
standard
deviation
for
three
replicates.
of
determination
for
6 standards
(0.05–100
?g l−1).
from
S/N
= 3.
from
S/N
= 10.
Table
Enrichment
2
factor,
relative
recovery
and
reproducibility
of
the
method.
Analytes

Enrichment
factora
RR
(%)b(5 ?g l−1spiked)

%RSD
(n = 3)
1,3,5-TCB
1,2,3-TCB
HCBD
TCMB
1,2,3,4-TeCB
1,2,4,5-TeCB
PeCB
HCB

25
84.9
86.8
102.4
79.3
88.5
110.1
79.0
72.9
8.8
10.9
3.5
8.1
7.7
6.3
6.2
9.2

336
80
268
382
43
36
1008







aCalculated
bRelative
by taking
the
ratio
of
peak
area
for
the
extract
of
spiked
water
sample
to that
of
un-extracted
sample.
recovery:
recovery
of
spiked
tap water
sample
relative
to that
of spiked
ultra
pure
water.
Consequent
tion
to this
observation,
methanol
was
chosen
for
applica-
in further
experiments.
3.4.
Effect
of
pH
As
presented
in Fig.
3,
effect
of different
sample
pH (2,
4, 7,
9
and
some
(pH
functionality
the
ral
insecticides
sorption
brane
Considering
ing
12)
values
on
the
extraction
procedure
was
also
tested.
While
analytes
performed
relatively
better
at pH other
than
neutral
= 7),
the
overall
effect
seems
to favor
the
neutral
pH at which
the
of
the
native
polymer/membrane
for
sorption
toward
analytes,
in general,
was
optimal.
This
effect
mimics
the
natu-
setting
in which
bio-concentration
of
chlorinated
hydrocarbon
was
optimal
at pH 7 [35]. This
may
be
due
to enhanced
of
the
analytes
from
water
to the
surface
of
bacterial
mem-
containing
phosphate
groups
in membrane
phospholipids.
this
result,
ultrapure
water
(pH
= 7)
was
used
for
spik-
in subsequent
extraction
procedures
for
method
optimization.
Fig.
50
as
3.
Effect
of
pH variation
on
the
peak
areas
of
CHCs
at experimental
conditions
of
min
extraction
and
5 min
desorption,
with
PPSU-A
0.75
as sorbent
and
methanol
solvent.
4. Method
appraisal
To
evaluate
the
performance
of
this
method,
50 mg
piece
of
the
functionalized
CHCs
of
concentrations
determination
lytes
LODs
signal-to-noise
showed
general
its
and
of
enrichment
this
The
documented
SDME-GC–MS
LPME-GC–MS
SDME-thermal
microwave
microextractin
extraction
time,
These
for
CHCs
ysis
water
in
with
nal
were
detected
Table
polymer/membrane
was
used
for
the
extraction
of
from
ultrapure
water
spiked
with
different
concentrations
the
analytes.
Good
linearity
was
established
over
wide
range
of
(0.05–100
?g
l−1) as
signified
by the
coefficients
of
(r2) between
0.9954
and
0.9999
for
the
eight
ana-
under
investigation
(Table
1).
for
the
different
compounds
were
calculated
based
on the
(S/N)
ratio
of
3.
The
tetrachlorinated
hydrocarbons
lower
values
compared
to other
analytes.
However,
the
LODs
calculated
in ng
l−1(0.4–3.9)
and
the
estimated
lim-
of
quantitation
(LOQ)
of 1.3–13.0
ng
l−1indicate
high
sensitivity
suitability
of the
method
for
the
quantitative
determination
all
the
analytes
in water
matrix.
The
extraction
method
high
factor
(25-1008)
(Table
2,
Fig.
4)
has
contributed
to
sensitivity.
developed
?-SPE
method
compared
favorably
with
ones
in the
literature,
including
head-space
(HS)-
[36], SPE-GC–MS
[37], LLE-GC-ECD
[38], and
[39], SPME-GC-ECD
[40], ionic-liquid
(IL)-HS-
desorption
(TD)-GC–MS
[41], SPME-GC–MS
[42],
(MW)-HS-SDME-HPLC
[43], dispersive
liquid–liquid
(DLLME)-GC-ECD
[44]
and
headspace
sorptive
(HSSE)-GC–MS
[45]
based
on
sample
volume,
extraction
LOD
and
%RSD
as
presented
in Table
3.
results
stress
the
rapidity
of this
method
and
its
suitability
application
as
a viable
and
reproducible
means
of
determining
in water.
Furthermore,
the
method
was
applied
to the
anal-
of
CHCs
in real
water
samples
from
six
sources:
three
bottled
samples
and
three
tap
water
samples.
CHCs
were
detected
all
water
samples.
One
of
the
samples
(tap
water)
was
spiked
5 ?g
l−1of
CHCs
and
recoveries
were
calculated
using
exter-
calibration.
Recoveries
were
between
73 and
110%
and
%RSDs
calculated
between
3.5
and
10.9%.
The
quantities
of
CHCs
and
quantified
within
the
method
LODs
are
presented
in
4.

Page 5

288
A.A.
Nuhu
et
al.
/ Talanta
87 (2011) 284–
289
Fig.
(3)
4. Chromatograms
of
(a)
10
?g ml−1of
analyte
mixed
standards,
and
(b)
spiked
100
?g l−1water
sample
extract
after
peak
identification:
(1)
1,3,5-TCB,
(2)
1,2,3-TCB,
HCBD,
(4)
TCMB,
(5)
1,2,3,4-TeCB,
(6)
1,2,4,5-TeCB,
(7)
PeCB,
and
(8)
HCB.
Table 3
Method
performance
as
compared
with
literature
results.
MethodSample
volume
(ml)Extraction
time
(min)

LOD
(ng
l−1)
%RSD

Reference
HS-SDME-GC–MS
SPE-GC–MS
LLE-GC-ECD
LPME-GC–MS
SPME-GC-ECD
IL-HS-SDME-TD-GC–MS
SPME-GC–MS
MW-HS-SDME-HPLC
DLLME-GC-ECD
HSSE-GC–MS
?-SPE-GC–MS

10
200
4000

5
3–31
10–45
0.01–500
20–50
0.32–2.25
1–4
0.004–0.02
16–39
0.5–50
2–120
0.4–3.9

2.1–13.2
1.6–13.3
10
1.6–17.9
2.1–4.9
2–17
2.7–4.9
1.7–12
0.52–6
5–10
3.5–10.9

[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
This

∼=50
>240



4
5
3.5
15
37
30
20
≤1
60
50



10
10
30
5
50
10





work
Table
Organochlorines
4
in bottled
and
tap
water
sources
of
Saudi
Arabia.
Analytes

Concentration
SHIFA
(?g l−1)a,b

NOVA

AFNAN

Khafji

Riyadh

Rastanura
1,3,5-TCB
1,2,3-TCB
HCBD
TCMB
1,2,3,4-TeCB
1,2,4,5-TeCB
PeCB
HCB

0.16
NDc
0.59
0.20
ND
ND
0.89
0.99
± 0.01

0.34
ND
0.46
0.31
ND
ND
1.55
1.33
± 0.03

0.09
ND
0.63
0.47
ND
ND
1.66
1.49
± 0.01

0.18
ND
0.81
1.07
ND
ND
2.10
2.17
± 0.02

0.45
ND
0.53
0.92
0.05
ND
2.01
1.74
± 0.04

0.11
ND
0.70
0.30
ND
ND
2.19
2.19
± 0.01

± 0.02
± 0.02
± 0.02
± 0.03
± 0.02
±
0.03
± 0.02
± 0.03
± 0.04
± 0.09
± 0.07
±
0.02
± 0.01


± 0.05
± 0.1
± 0.1
± 0.13
± 0.14
±
0.13
± 0.09
± 0.12
± 0.14
± 0.2
± 0.16
±
0.2
aMean
bSHIFA,
cNot
± SD for
three
determinations.
NOVA
and
AFNAN
are
bottled
water
sources
while
Khafji,
Riyadh
and
Rastanura
are
tap
water
sources.
detected.

Page 6

A.A.
Nuhu
et al.
/ Talanta
87 (2011) 284–
289
289
The
highest
value
for
the
bottled
water
was
obtained
in the
AFNAN
was
Province
Mixing
levels
area
carbon
so,
tap
On
commonly
respectively,
the
mination,
contaminant
to the
sample.
This
was
followed
by
NOVA,
and
the
lowest
value
in SHIFA,
with
source
from
Al-Hasa,
an
area
in the
Eastern
of
Saudi
Arabia
which
harbors
the
world’s
largest
oasis.
and
dilution
phenomena
might
have
contributed
to its
low
of
CHCs.
For
the
tap water
analysis,
the
sample
from
Khafji,
an
between
Saudi
Arabia
and
Kuwait
where
an immense
hydro-
activity
has
been
going
on
for
the
last
three
decades
or
has
the
highest
percentage
of
the
detected
CHCs.
The
Riyadh
water
has
slightly
lower
concentration
than
that
of
Rastanura.
the
other
hand,
the
penta-
and
hexachlorinated
hydrocarbons,
used
in agriculture
as
pesticide
and
for
seed
dressing,
account
for
more
than
70%
of
the
detected
CHCs.
While
values
obtained
for
tap
water
analysis,
within
the
error
of
deter-
may
be
slightly
above
the
current
1 ?g l−1maximum
level
(MCL)
for
HCB
[46], none
of
the
TCBs
came
close
70 ?g l−1stipulated
for
1,2,4-trichlorobenzene.
5.
Conclusions
In
this
investigation,
we
have
developed
a simple
and
efficient
?-SPE
phosphonic
sorbents.
aromatic
donor–acceptor
aromatic
Various
obtained
time,
solvent.
pH.
PPSU-A
of
The
(0.05–100
values,
analytes
formances
recovery
method
method
for
the
analysis
of
CHCs
in water
matrix
using
novel
acid/ester
functionalized
polysulfone
membranes
as
The
membranes
provided
good
sorption
ability
for
the
CHCs
due
to enhanced
hydrophilicity
and
? electron
interactions
between
the
polymeric
matrix
and
the
analytes.
factors
governing
extraction
have
been
studied.
Results
indicate
the
optimized
conditions
as
50
min
extraction
5 min
desorption
time
and
the
use
of
methanol
as
desorption
Enhanced
extraction
recoveries
were
obtained
at
neutral
The
polymeric
membrane
that
showed
the
best
result
was
0.75,
due
to non
cross-linked
backbone
and
the
presence
phosphonic
acid
functionality.
method
response
was
found
to be linear
within
wide
range
?g l−1) of analyte
concentrations
as
signified
by
the
r2
and
its
very
low
LOQ
values
have
allowed
quantitation
of
in real
samples
at sub
part-per-billion
levels.
These
per-
and
all
other
appraisal
indices
such
as
LOD,
relative
and
%RSD
indicate
the
suitable
applicability
of
the
present
in the
analysis
of
real
water
samples.
Acknowledgments
The
authors
would
like
to acknowledge
the
funding
support
of
IN100003)
sampling.
the
Deanship
of
Scientific
Research
at KFUPM
(project
no:
and
thank
Mr.
Ayman
Al-Majid
for
assisting
with
water
References
[1]
[2] V.
A.
Tor,
J. Chromatogr.
A 1125
(2006)
129.
Goutner,
P.H.
Becker,
V.
Liordos,
Sci.
Total
Environ.
409
(2011)
710.
[3]
M.M.
eroso,
Ulaszewska,
E.
Zuccato,
E. Capri,
R.
Iovine,
A.
Colombo,
G.
Rotella,
C. Gen-
P.
Grassi,
M.
Melis,
R.
Fanelli,
Chemosphere
82
(2011)
1.
[4]
[5] C. Matthai,
[6] D.A.
(1995)
[7]
Gabrielsen,
[8] D. Bagga,
(2000)
[9]
142.
[10] P. Zhou,
Environ.
[11]
1179.
[12] J.A.
101 (2011)
[13]
Toxicol.
[14] G.
[15]
M.
[16] L.L.
[17] R.M.
96
[18]
Cogolludo,
[19]
[20] D.A.
95.
[21] K.G.
[22]
[23] B. Tienpont,
577.
[24] L.C.
[25] C. Basheer,
(2011) 654.
[26]
[27] L.
[28]
[29]
Diels,
[30] I.
[31] O.
Sci.
[32]
[33] A.Y.
[34] A.J.
Chem.
[35] D.J.
[36] L.
[37] Y.
[38] B.G.
[39] Y. Wang,
[40]
[41] A.
1290.
[42]
S.
[43] L.
9.
[44]
(2007)
[45]
393
[46]
epa.gov/drink/contaminants/index.cfm>.
Y. Su,
H.
Hung,
Environ.
Pollut.
158
(2010)
3365.
G.F.
Birch,
Environ.
Pollut.
110
(2000)
411.
Bright,
W.T.
Dushenko,
S.L.
Grundy,
K.J.
Reimer,
Sci.
Total
Environ.
160/161
265.
J.O.
Bustnes,
B.
Moe,
D.
Herzke,
S.A.
Hanssen,
T.
Nordstad,
K.
Sagerup,
G.W.
K.
Borgå,
Chemosphere
79
(2010)
320.
K.H.
Anders,
H-J.
Wang,
E. Roberts,
J.A.
Glaspy,
J. Natl.
Cancer
Inst.
92
750.
H.L.
Tsang,
S.
Wu,
C.K.M.
Leung,
S.
Tao,
M.H.
Wong,
Environ.
Int.
37
(2011)
Y.
Wu,
S.
Yin,
J. Li,
Y.
Zhao,
L.
Zhang,
H.
Chen,
Y.
Liu,
X.
Yang,
X.
Li,
Pollut.
159
(2011)
524.
A.
Fromberg,
K.
Granby,
A.
Højgård,
S.
Fagt,
J.C.
Larsen,
Food
Chem.
125
(2011)
Scott,
J.P.
Incardona,
K.
Pelkki,
S.
Shepardson,
P.V.
Hodson,
Aquat.
Toxicol.
165.
T.S.
Chan,
J.X.
Wilson,
S.
Selliah,
M.
Bilodeau,
C.
Zwingmann,
R. Poon,
P.J.
O’Brien,
Appl.
Pharmacol.
232
(2008)
456.
Toft,
L.
Hagmar,
A.
Giwercman,
J.P.
Bonde,
Reprod.
Toxicol.
19 (2004)
5.
T. Kunisue,
M.
Watanabe,
A.
Subramanian,
A.
Sethuraman,
A.M.
Titenko,
V.
Qui,
Prudente,
S.
Tanabe,
Environ.
Pollut.
125
(2003)
157.
Qian,
Y.-Z.
He,
J. Chromatogr.
A 1134
(2006)
32.
Cavalcante,
M.V.F.
de
Andrade,
R.V.
Marins,
L.D.M.
Oliveira,
Microchem.
J.
(2010)
337.
J.J.B.
Nevado,
R.C.R.
Martín-Doimeadiós,
F.J.G.
Bernardo,
N.R.
Farinas,
J.M.G.
J.A.C.
Osma,
Talanta
81
(2010)
887.
J. Dreiucker,
W.
Vetter,
Food
Chem.
126
(2011)
762.
Lambropoulou,
T.A.
Albanis,
J. Biochem.
Biophys.
Methods
70 (2007)
Drouillard,
H.
Hagen,
G.D.
Haffner,
Chemosphere
55
(2004)
395.
H.-P.
Li,
C.-H.
Lin,
J.-F.
Jen,
Talanta
79
(2009)
466.
F. David,
C.
Bicchi,
P. Sandra,
J. Microcolumn
Sep.
12 (11)
(2000)
Lu,
C.I.
Wang,
W.F.
Sye,
Carbohydr.
Polym.
83
(2011)
1984.
G.
Balaji,
S.H.
Chua,
S.
Valiyaveettil,
H.K.
Lee,
J. Chromatogr.
A 1218
S.I.
Semenova,
J. Membr.
Sci.
231
(2004)
189.
Benoît,
P. Mario,
J. Patric,
Macromol.
Rapid
Commun.
26
(2005)
1464.
B. Van
der,
Bruggen,
J. Appl.
Polym.
Sci.
114
(2009)
630.
L.
Bastiaens,
D.
Springael,
P. Wattiau,
H.
Harms,
R.
deWachter,
H.
Verachtert,
L.
Appl.
Environ.
Microbiol.
66 (2000)
1834.
Cabasso,
Ind.
Eng.
Chem.
Prod.
Res.
Dev.
22
(1983)
313.
Ken-ichi,
W. Hongyuan,
I. Takeo,
F. Sachie,
T.
Kazuhiro,
K.
Hidetoshi,
J.
Membr.
157
(1999)
97.
H.R.
Acharya,
S.A.
Stern,
Z.Z.
Liu,
I. Cabasso,
J. Membr.
Sci.
37
(1988)
205.
Nedal,
S.A.
Ali,
S.M.
Javaid
Zaidi,
J. Membr.
Sci.
360
(2010)
26.
Fletcher,
E.J.
Cussen,
D.
Bradshaw,
M.J.
Rosseinsky,
K.M.
Thomas,
J. Am.
Soc.
126
(2004)
9750.
Grimes,
S.M.
Morrison,
Microb.
Ecol.
2 (1975)
43.
Vidal,
A.
Canals,
N.
Kalogerakis,
E. Psillakis,
J. Chromatogr.
A 1089
(2005)
25.
Wang,
H.K.
Lee,
J. Chromatogr.
A 803
(1998)
219.
Oliver,
K.D.
Bothen,
Anal.
Chem.
52
(1980)
2066.
Y.
Chian
Kwok,
Y.
He,
H.K.
Lee,
Anal.
Chem.
70
(1998)
4610.
X.-J.
Li,
C.-W.
Ye,
X.-L.
Huo,
Z. Zeng,
Mikrochim.
Acta
168
(2010)
161.
Chisvert,
I.P.
Román,
L.
Vidal,
A.
Canals,
J. Chromatogr.
A 1216
(2009)
F. Bianchi,
M.
Mattarozzi,
P. Betti,
F. Bisceglie,
M.
Careri,
A.
Mangia,
L.
Sidisky,
Ongarato,
E. Dalcanale,
Anal.
Chem.
80
(2008)
6423.
Vidal,
C.E.
Domini,
N.
Grane,
E.
Psillakis,
A.
Canals,
Anal.
Chim.
Acta
592
(2007)
R.R.
Kozani,
Y.
Assadi,
F. Shemirani,
M.-R.M.
Hosseini,
M.R.
Jamali,
Talanta
72
387.
M.S.
van
Pinxteren,
L.
Montero,
S.
Jäsch,
H.
Paschke,
P.
Popp,
Anal.
Bioanal.
Chem.
(2009)
767.
[EPA]
Environmental
Protection
Agency.
Available
from:
<http://water.
Accessed
February,
2011.