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Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

Preparation and characterization of metal-organic framework

MIL-101(Cr)-coated solid-phase microextraction ber
Lijun Xie, Shuqin Liu, Zhubing Han, Ruifen Jiang, Hong Liu *, Fang Zhu, Feng Zeng,
Chengyong Su, Gangfeng Ouyang *
MOE Key Laboratory of Aquatic Product Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen
University, Guangzhou 510275, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

 MIL-101(Cr)-coated SPME ber was

prepared and characterized.
 Diluted silicone sealant was used for
preparing the ber by layer-by-layer.
 The ber exhibited excellent extrac-
tion performance for BTEX and PAHs.

A R T I C L E I N F O A B S T R A C T

Article history: Metal-organic frameworks (MOFs) have received great attention as novel sorbents due to their fascinating
Available online xxx structures and intriguing potential applications in various elds. In this work, a MIL-101(Cr)-coated solid-
phase microextraction (SPME) ber was fabricated by a simple direct coating method and applied to the
determination of volatile compounds (BTEX, benzene, toluene, ethylbenzene, m-xylene and o-xylene) and
Keywords: semi-volatile compounds (PAHs, polycyclic aromatic hydrocarbons) from water samples. The extraction
Metal-organic frameworks
and desorption conditions of headspace SPME (HS-SPME) were optimized. Under the optimized
Material Institute Lavoisier (MIL)-101(Cr)
conditions, the established methods exhibited excellent extraction performance. Good precision (<7.7%)
Solid-phase microextraction
Volatile compounds
and low detection limits (0.321.7 ng L 1 and 0.122.1 ng L 1 for BTEX and PAHs, respectively) were
achieved. In addition, the MIL-101(Cr)-coated ber possessed good thermal stability, and the ber can be
reused over 150 times. The ber was successfully applied to the analysis of BTEX and PAHs in river water by
coupling with gas chromatographymass spectrometry (GCMS). The analytes at low concentrations (1.7
and 10 ng L 1) were detected, and the recoveries obtained with the spiked river water samples were in the
range of 80.0113% and 84.8106% for BTEX and PAHs, respectively, which demonstrated the applicability
of the self-made ber.
2014 Elsevier B.V. All rights reserved.

1. Introduction sample preparation prior to analysis. It has received great attention

Solid-phase microextraction (SPME), introduced by Arthur and
Pawliszyn [1], is one of the most popular green techniques used for
* Corresponding authors. Tel.: +86 20 84110845; fax: +86 20 84110845.
E-mail addresses: liuhong@cigit.ac.cn (H. Liu), cesoygf@mail.sysu.edu.cn
(G. Ouyang).
as a powerful sample preparation technique due to its fast, simple,
sensitive and less solvent consumption characteristics. Besides,
owing to it is easy to be automated and available to be coupled with
gas chromatography (GC) or high performance liquid chromatog-
raphy (HPLC), SPME technique has been successfully applied to
environmental, biological, clinical and food analysis [210]. In
SPME, ber coating is considered to be the key factor. During the
past two decades, a lot of efforts have been made to develop novel

http://dx.doi.org/10.1016/j.aca.2014.09.048
0003-2670/ 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: L. Xie, et al., Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase
microextraction ber, Anal. Chim. Acta (2014), http://dx.doi.org/10.1016/j.aca.2014.09.048
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SPME coating materials with remarkable chemical and thermal
stability, enhanced sensitivity and selectivity for the specied
analytes [1115].
Metal-organic frameworks (MOFs) or porous coordination
polymers (PCPs), as a new class of hybrid inorganicorganic
microporous crystalline materials, have received considerable
attention. The unique features of MOFs, such as permanent nano-
scale porosity, higher surface area, uniform but tunable pore size,
make MOFs very intriguing materials for separation, gas storage,
catalysis, sensing, and imaging [1622]. Inspiringly, a few MOFs
have been either directly used or engineered to meet the demands
of various analytical applications [2325]. There also have been
some examples of utilization of various MOFs for SPME [2632].
MOF-199 [26], ZIF-8 [27], MIL-53(Al) [28], MAF-X8 [29], ZIF-90
[30], and MIL-88B [31] have been applied for the SPME of diverse
analytes.
Material Institute Lavoisier (MIL)-101(Cr), rst reported by
Ferey et al. [33], with a hybrid supertetrahedral building unit
constructed by terephthalate ligands and trimeric chromium
octahedral clusters, has high surface area, two types of mesoporous
cages (29 and 34 in diameter) [34], and excellent chemical,
hydrothermal stability. These features, in addition to the potential
for generation of unsaturated chromium(III) sites in the framework
on activation, make MIL-101(Cr) particularly attractive for practical
applications involving selective gas adsorption, separation and
heterogeneous catalysis [3438]. In analytical technology, it has
been applied as a stationary phase of GC capillary column to
successfully separate the xylene isomers and ethylbenzene [39,40].
Besides, MIL-101(Cr) was employed as the stationary phase for
HPLC to separate substituted aromatic [41], polar compounds [42]
and fullerene [43]. Sensitive probing of adsorption characteristic of
volatile organic compounds (VOCs) on MIL-101(Cr) by quartz
crystal microbalance [44] and a facile magnetization of MOF MIL-
101 for rapid magnetic solid-phase extraction (MSPE) of polycyclic
aromatic hydrocarbons (PAHs) were also reported [45]. Recently,
MIL-101(Cr) was fabricated in a polyetheretherketone (PEEK) tube
as micro-trapping device, and successfully applied to the analysis
of naproxen and its metabolite in human urine [46].
In this work, we introduced MIL-101(Cr) as a novel SPME ber
coating material for the sampling and analysis of VOCs, benzene,
toluene, ethylbenzene, o-xylene and m-xylene (BTEX), and semi-
VOCs, PAHs.
2. Experimental
2.1. Chemicals
Cr(NO3)3
9H2O (Kermel Chemical Reagent Co., Ltd., Tianjin,
China) and terephthalic acid (Jingchun Reagent, Shanghai, China)
were used to prepare MIL-101(Cr). N,N-Dimethylformamide
(DMF), sodium chloride (NaCl), ethanol, methanol, acetone and
hydrouoric acid of analytical grade were purchased from
Guangzhou Chemical Regent Factory (Guangzhou, China). Sika-
sil-C neutral multifunctional silicone sealant was purchased from
Shanghai Cheng Shen Decoration Material Company (Shanghai,
China). Ultrapure water was obtained from Millipore water
purication system (Billerica, MA, USA).
The stainless-steel wires (i.d. 127 mm) were purchased from
Component Supply Co. (Fort Meade, MD, USA) and cut into 3 cm
sections to prepare the bers. The SPME device was purchased
from Supelco (Bellefonte, PA, USA).
BTEX (benzene (99.5%), toluene (99.5%), ethylbenzene (99.5%),
m-xylene (99%), o-xylene (99%)), were purchased from Sigma
Aldrich Company (St. Louis, MO, USA). Five PAH standards,
naphthalene (99.5%), acenaphthene (99.5%), phenanthrene
(99.5%), uoranthene (98.5%), pyrene (99%), were purchased from
Please cite this article in press as: L. Xie, et al., Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase
microextraction ber, Anal. Chim. Acta (2014), http://dx.doi.org/10.1016/j.aca.2014.09.048
Dr. Ehrenstorfor GmbH (Germany). The stock solutions for two
types of analytes, BTEX or PAHs, were individually prepared in
methanol and dichloromethane at a concentration of 1 mg mL 1
for each of the analytes and stored in the dark at 4  C for further
use. The working standard solutions were prepared weekly by
diluting the standard solution with methanol, and more diluted
working solutions were prepared daily by diluting this standard
solution with pure water.
2.2. Instrumentations
Scanning electron microscopy (SEM) images were conducted by
a Quanta 400 Thermal FE Environment Scanning Electron
Microscope instrument (FEI, Netherlands). The surface images of
the MIL-101(Cr) coating were obtained at 20 kV. Thermal
gravimetric (TG) analysis was performed to evaluate the thermal
stability of the coating from room temperature to 500  C in owing
N2 at a heating rate of 10  C by STA449F3 (Netzsch, Germany).
The optimization procedure of SPME was conducted with an
Agilent 7890 GC-FID (Agilent, Palo Alto, CA, USA). The GC was
equipped with split/splitless injector and splitless mode was
chosen. A HP-5 capillary column (30 m  0.32 mm i.d.  0.25 mm
lm thickness) was used for separation. Nitrogen (99.999%) was
used as carrier and make-up gas. The ow rates of carrier gas and
make-up gas were 1.2 mL min 1 and 20 mL min 1, respectively.
Hydrogen (99.999%) was used as fuel gas and the ow rate was
30 mL min 1. The quantitative analytical performance of HS-SPME
method was determined with a GCMS (Agilent 6890 GC-
5975 Mass Spectrometer, Palo Alto, CA, USA), equipped with a
HP-5-MS capillary column (30 m  0.32 mm i.d.  0.25 um lm
thickness). Helium (99.999%) was employed as carrier gas and its
ow-rate was adjusted to 1.2 mL min 1. Both the GCFID and GC
MS were equipped with a GERSTEL MPS autosampler (GERSTEL,
Germany) to perform automatic SPME analysis.
The GCFID and GCMS shared the same column temperature
program. For BTEX, the column temperature program was set as
follows: initial 50  C (hold for 1 min), then ramped to 150  C at a
rate of 20  C min 1, and nally increased to 250  C at 50  C min 1
(held for 1 min). The column temperature program for PAHs was
set as follows: initial 50  C (hold for 0.5 min), then ramped to 150  C
at a rate of 20  C min 1, and again ramped at 15  C min 1 to 250  C
(hold for 6 min), nally increased to 270  C at 30  C min 1 (held for
8 min). To obtain the highest sensitivity, the MS detection was
operated using time-scheduled SIM.
2.3. Synthesis of MIL-101(Cr)
MIL-101(Cr) was synthesized according to Ref. [33]. Typically,
1200 mg of Cr(NO3)3
9H2O was dissolved in 14.4 mL ultrapure
water, and then mixed adequately with terephthalic acid (498 mg)
and hydrouoric acid (0.5 mL). The above solution was transferred
into a Teon-lined bomb, which was then sealed and placed in an
oven at 220  C for 8 h. After being cooled to room temperature, the
resultant green ne crystals were washed thoroughly with DMF
and ethanol successively to remove the unreacted terephthalic acid
and other reagents. The procedure was repeated at least three
times. The green solid was then collected by centrifugation at
10,000 rpm for 5 min and evacuated in vacuum at 150  C for 24 h.
The MIL-101(Cr) was characterized by X-ray diffraction (XRD)
spectrometry, and thermal gravimetric analysis (TGA).
2.4. Fiber preparation
Before the preparation of the ber, the MIL-101(Cr) solid was
ground and ultrasounded in methanol solvent for an hour and
then air-dried to become very small powder. To prepare MIL-101
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(Cr)-coated SPME ber, the stainless steel wires were washed in
an ultrasonic bath with acetone, methanol, and distilled water,
and then air-dried. The pre-treated stainless steel wire was
perpendicularly dipped into silicone sealant, which was diluted
with toluene (w/v: 500 mg/1 mL) in a centrifuge tube, then pulled
out quickly. To ensure that the thickness of glue was very thin, the
superuous glue on the wire was removed by rotating the wire on
a piece of clean weighing paper. Later, the ber was vertically
inserted into the prepared MOFs powder in a centrifuge tube,
rotated a few cycles and pulled out. Subsequently, the coated ber
was placed in an oven for baking at 150  C for 30 min. The above
process was repeated several times, until the desirable thickness
was obtained. At last, the coated wire was dipped into the diluted
glue again to form a thin lm of polymer which can protect the
whole coating and avoid the aking of the powder. The coating
thicknesses obtained after three coating cycles were around
25 mm. All the prepared bers were placed in a desiccator
overnight at room temperature. Prior to use, 1 cm coating will be
left and the other coating will be scratched off. After that, the
coated wire was inserted into the inside needle of the ber
assembly for use. The prepared bers were then conditioned at
200  C and 250  C in a GC injection port under nitrogen for 1 h,
respectively.
2.5. SPME procedure
All of the bers were conditioned 30 min at 250  C before use.
Sample solutions were prepared by diluting working standard
solutions with pure water. A headspace mode was employed for
the extraction of analytes from 10 mL of water sample contained in
a 20 mL vial. The agitation of sample was xed at 500 rpm. All of the
extraction procedures, including the vial transfer, agitation,
extraction, injection were auto-performed with the Gerstel
autosampler using the Gerstel Maestro 1 software.
3. Results and discussion
3.1. Characterization of the MIL-101(Cr)-coated ber
The MIL-101(Cr) powder prepared for the MIL-101(Cr)-coated
bers was conrmed by comparing the XRD pattern of the
synthesized MIL-101(Cr) and the simulated one adopted from
literature [33]. The XRD pattern of the MIL-101(Cr) powder is in
good agreement with the simulated one (Fig. 1a), showing the
successful synthesis of MIL-101(Cr). Fig. 1b is the TG curve of the
MIL-101(Cr) powder. It can be noted that the initial weight loss
before about 100  C resulted from the removal of the solvent
methanol trapped within the pores and the MIL-101(Cr) can be
stable up to 400  C. The high thermal stability of the MIL-101(Cr) is
Fig. 1. (a) XRD pattern of simulated MIL-101(Cr) diffraction pattern and the synthesized MIL-101(Cr). (b) TG curve of the synthesized MIL-101(Cr) powder.
Please cite this article in press as: L. Xie, et al., Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase
microextraction ber, Anal. Chim. Acta (2014), http://dx.doi.org/10.1016/j.aca.2014.09.048
3
favorable for the thermal desorption of the adsorbed analytes from
the SPME ber for GC analysis.
Among various MOF coating methods for SPME, the in situ
growth method and the covalent bonding approach had drawn a
lot of interest. However, the two coating methods are usually
limited to special substrates. In the present study, the synthesized
MIL-101(Cr) nanoparticles were directly pasted on the stainless
steel wire with diluted silicone sealant. Using this method, strong
linkages including coating-to-substrate and layer-to-layer linking
would form, generating a robust hybrid MOF based coating. The
SEM image of the MIL-101(Cr) coating revealed that the coating
possessed a homogeneous surface and the thickness of the coating
was about 25 mm (Fig. 2a). Moreover, Fig. 2bd shows that MIL-101
(Cr) had been successfully immobilized on the stainless steel wire
and the powder had been linked together layer-by-layer, while the
glue layer is very thin and nearly invisible. Therefore, this direct dip
coating method can both maintain the unique characteristic of
MIL-101(Cr) powder and avoid the dropping off of the powder from
the coating substrate.
3.2. Optimization of extraction condition
There are various factors affecting the extraction efciency of
the MIL-101(Cr) coated ber, such as extraction time and
temperature, desorption time and temperature, or salt concentra-
tion. To achieve the best extraction performance of the self-made
ber, these factors were investigated and optimized.
The effect of extraction time on the extraction efciency of BTEX
and PAHs were investigated from 1 to 9 min (Fig. 3a) and from 20 to
40 min (Fig. 3b), respectively. For BTEX, the peak areas of benzene
and toluene were decreased with the increasing of extraction time
before 3 min, while ethylbenzene, m-xylene, o-xylene presented
an opposite tendency. The extraction equilibrium occurred at
3 min for all BTEX. For ve PAHs (Fig. 3b), to achieve the best
extraction efciency, 30 min was chosen as the extraction time.
Extraction temperature affects both the release of the analytes
from aqueous sample into headspace and the adsorption of the
analytes in headspace onto the SPME ber. In general, increasing
extraction temperature can facilitate the mass transfer of analytes
from water to headspace, giving a higher concentration of analytes
in headspace and better extraction efciency. The effect of
extraction temperature of BTEX was studied from 30  C to 45  C
(Fig. 3c). An extraction temperature of 35  C was chosen for the
following experiments. As shown in Fig. 3d, the extraction
efciencies of naphthalene and acenaphthene decreased after
the temperature higher than 50  C. Thus, 50  C was selected as the
extraction temperature.
Proper desorption time and temperature must be chosen to
release analytes sufciently from the MIL-101(Cr)-coated ber. The
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Fig. 2. SEM images of the fabricated MIL-101(Cr)-coated SPME ber. (a) 500 (b) 1500 (c) 3000 (d) 8000 magnication.

effects of desorption time were investigated from 2 to 6 min
(presented in Fig. S1a and b). For both BETX and PAHs, 3 min was
the best desorption time. The effect of desorption temperature was
also investigated from 240  C to 270  C (Fig. S1c and d). The results
showed that 250  C was the optimal desorption temperature for
both BETX and PAHs.
Salting is one of the common techniques used to enhance
extraction of organics from aqueous solutions. Sodium chloride is
commonly used for this purpose. For PAHs, the solubility in the
water will decrease with increased amount of sodium chloride. In
our work, salt concentrations ranged from 0 to 25% (m/v) were
investigated only for PAHs (Fig. S2), considering they are semi-
VOCs. The prole showed that the best extraction performance was
obtained at salt concentration of 15%.
3.3. The stability of the MIL-101(Cr)-coated ber
The thermal stability of the MIL-101(Cr)-coated ber was tested
by aging at 300  C with nitrogen in the GC injection port for 3 h. The
ber was subjected to further experiment under optimized
conditions. The comparison of the extraction efciencies of the
treated and untreated SPME ber for BTEX and PAHs were shown
in Fig. S3. The extraction efciencies of the MIL-101(Cr)-coated
ber kept constant after treated under high temperature, which
demonstrated the thermal stability of the MIL-101(Cr)-coated
ber. In addition, our experiments results also indicated that the
MIL-101(Cr)-coated ber can be reused over 150 times without
signicant changes in extraction performance under the experi-
mental conditions, which illustrated the long life-time of the self-
made ber.
3.4. Comparison of the MIL-101(Cr)-coated ber with commercial
PDMS ber
In order to evaluate the extraction performance of the self-made
25 mm MIL-101(Cr)-coated ber toward BETX and PAHs, commercial
30 mm PDMS ber was selected for the comparison. Fig. 4a showed
that the extraction efciencies of MIL-101(Cr)-coated ber for BTEX
were more than 10 times higher than those of the commercial ber,
and even 20 times for o-xylene. Similarly, Fig. 4b also showed that

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Fig. 3. The proles of extraction time and temperature of BTEX and PAHs.

the MIL-101(Cr)-coated ber exhibited excellent extraction perfor-
mance toward PAHs. The extraction efciencies of the self-made
ber were 2 times (phenanthrene, uoranthene and pyrene) to
38 times (naphthalene) higher than those of the commercial PDMS
ber.
The excellent performance of MIL-101(Cr) for BTEX and PAHs
likely resulted from the pp interactions of the aromatic rings of
the analytes with the framework 1,4-benzenedicarboxylic acid
molecules, and the p-complexation of the electron-rich analytes to
the Lewis acid sites in the pores of MIL-101(Cr). For the PAHs, we

Fig. 4. Extraction efciency comparison of the 25 mm MIL-101(Cr)-coated ber and the commercial 30 mm PDMS ber. Concentration of each BTEX is 600 mg L 1, each PAH is
10 mg L 1.

Please cite this article in press as: L. Xie, et al., Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase
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Table 1
Linear ranges, correlation coefcients, detection limits, and repeatabilities, reproducibilities of the proposed SPMEGCMS methods using MIL-101(Cr)-coated ber.
1
Compounds Linear range (ng L ) Correlation coefcient (R2) LOD (ng L 1
) Repeatability (%, n = 6) Fiber to ber reproducibility (%, n = 3)
Benzene 1020,000 0.9996 1.7 2.3 11
Toluene 1020,000 0.9968 1.4 2.1 7.5
Ethylbenzene 1020,000 0.9995 0.65 6.7 3.2
m-Xylene 1020,000 0.9975 0.81 5.3 6.6
o-Xylene 1020,000 0.9985 0.32 7.1 9.4
Naphthalene 10500 0.9983 0.12 3.1 8.3
Acenaphthene 10500 0.9952 0.27 1.2 3.9
Phenanthrene 10500 0.9928 0.44 3.4 3.3
Fluoranthene 10500 0.9914 2.1 4.9 7.6
Pyrene 10500 0.9986 2.0 3.8 6.5

Table 2
Comparison of LODs between the developed methods with other works.
1
Analytes Coating LOD (ng L ) Extraction time (min) Analytical method Reference
BTEX Vinyl-SBA-15 1077 30 GCMS [48]
BTEX Carbon 847 40 GCMS [49]
BTEX ZNRs/PANI 124 20 GCFID [50]
BTEX PDMS-IL-HT 0.12 30 GCFID [51]
BTEX CNTs sol-gel 0.50.7 35 GCMS [52]
BTEX PEG-g-MWCNTs 0.63 30 GCFID [53]
BTEX MOF-199 8.323.3 20 GCFID [26]
BTEX MAF-X8 660 8 GCFID [29]
BTEX MIL-101(Cr) 0.321.7 3 GCMS This work
PAHs Carbon nanoparticles 13 40 GCFID [54]
PAHs CNTTiO2 24 40 GCFID [55]
PAHs Graphite oxide 1.52.7 50 GCMS [56]
PAHs PPy/SBA15 420 20 GCMS [57]
PAHs Anilinesilica nanocomposite 13 25 GCMS [58]
PAHs IRMOF-3 12.015.4 30 GCFID [8]
PAHs MIL-53(Al) 0.100.24 30 GCMS/MS [28]
PAHs MIL-101(Cr) 0.122.1 30 GCMS This work

Table 3
Analytical results of the river water and the recoveries obtained with the spiked samples.
1 1 1
Compounds Detected amount (ng L ) Spiked amount (ng L ) Found amount (ng L ) Recoveries (%) RSD (%)
Benzene 1.7  0.08 10 11.6 99.0 0.3
50 50.3 97.2 9.7

Toluene nd 10 11.3 113 5.2

50 53.6 107 6.3

Ethylbenzene 2.1  0.04 10 13.4 80.0 4.4

50 49.1 94.1 4.1

m-Xylene 5.4  0.3 10 14.5 91.0 6.0

50 52.6 94.6 5.3

o-Xylene 2.6  0.08 10 13.0 104 9.7

50 58.3 111 2.7

Naphthalene nd 20 21.0 105 4.5

50 45.2 90.4 4.5

Acenaphthene 2.2  0.02 20 20.1 89.5 1.4

50 55.7 106 3.6

Phenanthrene nd 20 19.7 84.8 1.2

50 44.6 89.2 4.1

Fluoranthene 10.0  0.7 20 29.3 96.6 3.3

50 57.9 95.8 5.3

Pyrene 6.63  0.5 20 27.5 104 7.5

50 54.4 95.5 1.7

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cansee that the order of extraction efciency for ve analytes is in
good agreement with the order of the molecular diffusion
coefcients in air (Dia) of the PAHs (naphthalene > acenaphthene >
uorene > phenanthrene > uoranthene  pyrene). The calculation
results of Dia were 0.077, 0.067, 0.066, 0.063 and 0.064 cm2 s 1 for
naphthalene, acenaphthene, uorine, phenanthrene, uoranthene
and pyrene, respectively [47]. The results indicated that the
molecular diffusion speed in air of the analytes probably is the
main factor for the selectivity of the adsorption.
3.5. Method evaluation and real sample application
The calibration curves, limits of detections (LODs), correlation
coefcients, and repeatabilities were determined under the opti-
mized conditions for BTEX and PAHs analysis. Table 1 presents a
summary of the gures of merit of the optimized SPMEGCMS
analysis method using the MIL-101(Cr)-coated ber. The linearity
was measured by spiked stand solutions with different concen-
trations (1020,000 ng L 1 for ve BTEX and 10500 ng L 1 for ve
PAHs). The correlation coefcients (R2) were found to be 0.9968
0.9995 for BTEX and 0.99140.9986 for PAHs. The LODs were found
to be in the range of 0.321.7 ng L 1 for BTEX and 0.122.1 ng L 1 for
PAHs at a signal to noise (S/N) of 3. The repeatabilities obtained from
six replicate samples ranged from 2.1 to 6.7% for BTEX and 1.24.9%
for PAHs, and the reproducibilities obtained with three bers ranged
from 3.2 to 11% for BTEX and 3.38.3% for PAHs. The LODs for BTEX
and PAHs obtained with the MIL-101(Cr)-coated ber were lower or
close to those recently reported results (Table 2).
The methods were applied to the BTEX and PAHs analysis in
spiked and no spiked water samples collected from the Pearl River,
Guangzhou, China. The results are given in Table 3. Several analytes
were found in the water samples. The concentrations of the detected
analytes were between 1.7 and 10 ng L 1. Then, the samples were
spiked with concentrations of 10 ng L 1 and 50 ng L 1 for ve BTEX
and 20 ng L 1 and 50 ng L 1 ve PAHs. Good recoveries were
obtained, which ranged from 80.0% to 113% for BTEX and 84.8
106% for PAHs.
4. Conclusion
A thermal stable MIL-101(Cr)-coated SPME ber was prepared
and characterized in this study. The MIL-101(Cr) powder was
synthesized and characterized by XRD and TG. A toluene diluted
silicone sealant was used for the preparation of the MIL-101(Cr)-
coated ber by layer-by-layer method. The self-made ber exhibited
excellent extraction efciency, good stability, wide linear range and
good reproducibility for the extraction of BTEX and PAHs in water
samples. Long lifetime of the MIL-101(Cr)-coated ber also
suggested the potential applicability in real sample applications.
Acknowledgments
We acknowledge nancial support from the projects of the
973 project (2012CB821701), NNSFC (21037001, 21225731), the NSF
of Guangdong Province (S2013030013474), and the Fundamental
Research Funds for the Central Universities (131gjc11).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.aca.2014.09.048.
References
[1] C.L. Arthur, J. Pawliszyn, Solid phase microextraction with thermal desorption
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