concentrate the analytes from the water samples. After the extraction procedure, the
fibers are inserted into the injection port of the gas chromatograph; the analytes are
thermo-desorbed from the fibers and then directly carried to the gas chromatographic
system by carrier gas for analysis. There are two main modes for solid-phase
microextraction, i.e. direct immersion and head-space solid-phase microextractions.
The former is mainly used for the extraction of the analytes with higher boiling
points and low volatility. The latter is mainly used for the extraction of the analytes
with higher volatility. Solid-phase microextraction has numerous advantages,
including (1) minimum or no solvent consumption, (2) small sample amount
requirement, (3) short sample preparation time, (4) simplified automation leading
to high-throughput analysis, (5) extraction and preconcentration of analytes from
solid, liquid, and gaseous sample matrices (Risticevic et al. 2009). In recent years,
solid-phase microextraction in combination with gas chromatography or gas
chromatography–mass spectrometry has been widely applied to the analysis of
numerous compounds, including phthalates. It was also introduced for direct coupling with high-performance liquid chromatography and ultra-performance liquid
chromatography coupled with tandem mass spectrometry in order to analyze
involatile or thermally labile compounds which are not amenable to gas chromatography or gas chromatography–mass spectrometry (Risticevic et al. 2009).
The main commercially available solid-phase microextraction heads include
non-polar polydimethylsiloxane, polar divinylbenzene/polyacrylate, and bipolar
diethylbenzene/carbon molecular sieve/polydimethylsiloxane. For the extraction of
phthalates in water samples, the most commonly used solid-phase microextraction
heads are polydimethylsiloxane/divinylbenzene (Cao 2008). Some new coating
materials have been reported for phthalates extraction in water, such as carbon
nanotubes (Luo et al. 2012; Song et al. 2016), polyaniline fiber (Li et al. 2006),
nano-TiO 2 fiber (Banitaba et al. 2013), polypyrrole-coated Fe 3 O 4 magnetic microsphere (Meng et al. 2011), Carbowax–divinylbenzene fiber (Luks-Betlej et al. 2001),
and mag-graphene@PDA (Wang et al. 2015a).
Luks-Betlej et al. (Luks-Betlej et al. 2001) compared the solid-phase
microextraction performances of six different non-polar and polar fibers for the
extraction of seven phthalates from drinking water. They concluded that 70 μm
Carbowax–divinylbenzene fiber was especially suitable for the extraction of the
selected phthalates.
Zhang et al. (2017) applied a probe of CNWBOND Si SPME to the extraction of
16 phthalates in sea water. The probe was immersed in 10 ml sample solution with
stirring at 500 rpm for 40 min at 35
C. After the extraction, the probe was thermally
desorbed for gas chromatography–mass spectrometric analysis. The limits of detection of the method were 0.005–0.32 μg/L, and the relative standard deviations were
0.24–8.8%. Liu et al. (2009) extracted 13 phthalates in lake water with 100 μ m
polydimethylsiloxane fibers and determined the phthalates by gas chromatography.
The limits of detection of the method were 0.02–0.83 μg/L, and the recovery rates
were 75.3–111.0%. Zhao et al. (2013) used bamboo charcoal as a fiber-coating
material for the extraction of 11 phthalates in environmental water samples and
determined by gas chromatography–mass spectrometry. The limits of detection were
15 Analytical Methods for Phthalates in Water Samples
553
fibers are inserted into the injection port of the gas chromatograph; the analytes are
thermo-desorbed from the fibers and then directly carried to the gas chromatographic
system by carrier gas for analysis. There are two main modes for solid-phase
microextraction, i.e. direct immersion and head-space solid-phase microextractions.
The former is mainly used for the extraction of the analytes with higher boiling
points and low volatility. The latter is mainly used for the extraction of the analytes
with higher volatility. Solid-phase microextraction has numerous advantages,
including (1) minimum or no solvent consumption, (2) small sample amount
requirement, (3) short sample preparation time, (4) simplified automation leading
to high-throughput analysis, (5) extraction and preconcentration of analytes from
solid, liquid, and gaseous sample matrices (Risticevic et al. 2009). In recent years,
solid-phase microextraction in combination with gas chromatography or gas
chromatography–mass spectrometry has been widely applied to the analysis of
numerous compounds, including phthalates. It was also introduced for direct coupling with high-performance liquid chromatography and ultra-performance liquid
chromatography coupled with tandem mass spectrometry in order to analyze
involatile or thermally labile compounds which are not amenable to gas chromatography or gas chromatography–mass spectrometry (Risticevic et al. 2009).
The main commercially available solid-phase microextraction heads include
non-polar polydimethylsiloxane, polar divinylbenzene/polyacrylate, and bipolar
diethylbenzene/carbon molecular sieve/polydimethylsiloxane. For the extraction of
phthalates in water samples, the most commonly used solid-phase microextraction
heads are polydimethylsiloxane/divinylbenzene (Cao 2008). Some new coating
materials have been reported for phthalates extraction in water, such as carbon
nanotubes (Luo et al. 2012; Song et al. 2016), polyaniline fiber (Li et al. 2006),
nano-TiO 2 fiber (Banitaba et al. 2013), polypyrrole-coated Fe 3 O 4 magnetic microsphere (Meng et al. 2011), Carbowax–divinylbenzene fiber (Luks-Betlej et al. 2001),
and mag-graphene@PDA (Wang et al. 2015a).
Luks-Betlej et al. (Luks-Betlej et al. 2001) compared the solid-phase
microextraction performances of six different non-polar and polar fibers for the
extraction of seven phthalates from drinking water. They concluded that 70 μm
Carbowax–divinylbenzene fiber was especially suitable for the extraction of the
selected phthalates.
Zhang et al. (2017) applied a probe of CNWBOND Si SPME to the extraction of
16 phthalates in sea water. The probe was immersed in 10 ml sample solution with
stirring at 500 rpm for 40 min at 35
C. After the extraction, the probe was thermally
desorbed for gas chromatography–mass spectrometric analysis. The limits of detection of the method were 0.005–0.32 μg/L, and the relative standard deviations were
0.24–8.8%. Liu et al. (2009) extracted 13 phthalates in lake water with 100 μ m
polydimethylsiloxane fibers and determined the phthalates by gas chromatography.
The limits of detection of the method were 0.02–0.83 μg/L, and the recovery rates
were 75.3–111.0%. Zhao et al. (2013) used bamboo charcoal as a fiber-coating
material for the extraction of 11 phthalates in environmental water samples and
determined by gas chromatography–mass spectrometry. The limits of detection were
15 Analytical Methods for Phthalates in Water Samples
553