ANALYTICAL SCIENCES OCTOBER 2004, VOL.

20 1383
2004 © The Japan Society for Analytical Chemistry

Determination of Polycyclic Aromatic Hydrocarbons in Water

by Solid-Phase Microextraction and Liquid Chromatography
Hong-Wen CHEN

Department of Environmental Engineering and Health, Yuanpei University of Science and Technology,
306 Yuanpei Street, Hsinchu 300, Taiwan R.O.C.

This study describes the determination of polycyclic aromatic hydrocarbons (PAHs) in water using high-performance
liquid chromatography (HPLC) coupled with fluorescence detection (FLD). Because individual PAHs are generally
present in water only at trace levels, a sensitive and accurate determination technique is essential. The separation and
detection of five PAHs were run completely within 25 min by the HPLC/FLD system with an analytical C18 column, a
fluorescence detection, and acetonitrile–water gradient elution. Calibration graphs were linear with very good correlation
coefficients (r > 0.9998), and the detection limits were in the range of 2 – 6 ng/l for five PAHs. Solid phase
microextraction (SPME) was performed for sample pretreatment prior to HPLC-FLD determination, and the governing
parameters were investigated. Compared to conventional methods, SPME has high recovery, saves considerable time,
and reduces solvents waste. The extraction efficiencies of five PAHs were above 88% and the extraction times were 35
min in one pretreatment procedure. One particular discovery is that 1.5 M sodium monochloroactate (ClCH2COONa) can
improve the extraction yield of PAH compounds more than other inorganic salts. The SPME-HPLC-FLD technique
provides a relatively simple, convenient, practical procedure, which was here successfully applied to determine five PAHs
in water from authentic water samples.

(Received May 14, 2004; Accepted August 10, 2004)

Several techniques for the extraction and concentration of

Introduction
Water pollution by organic compounds, many of which are
known to be toxic or carcinogenic, has caused considerable
concern worldwide. Coastal and inland water usually acts as
receptors for pollutants. Because streams, rivers, lakes, and
ponds are frequently used for potable water supplies, the
contamination of water sources is particularly undesirable.
Polycyclic aromatic hydrocarbons (PAHs), an important
group of organic pollutants in water, have received considerable
attention, because of their documented carcinogenicity in
experimental animals of several species.1 However, there are
several unsolved problems, including a practical analytical
technique. The US EPA has identified 16 PAHs as priority
pollutants, some of which reported as possible or probable
human carcinogens in IARC Monographs.2 Pathways for PAHs
to enter surface water include atmospheric fallout, urban run-
off, municipal effluents, industrial effluents, and oil spillage.
The presence of PAHs in drinking water may be due to surface
water used as raw water sources, which can potentially cause
risks to human health. Under standards3,4 adopted by the
European Union (EU) for drinking water, the limit of the
maximum concentration is 200 ng/l for PAHs. Because of this,
the determination of PAHs in environmental samples has
become an important topic, and the evaluation and monitoring
of trace levels of these compounds from authentic
environmental matrices are imperative. In order to determine
trace levels of ubiquitous environmental pollutants, effective,
clean-up extraction and procedures are usually necessary.
E-mail: hwchen@yust.edu.tw
PAHs from water and other phase materials are Soxhlet
extraction (SE), ultrasonic extraction (UE), liquid-liquid
extraction (LLE), solid-phase extraction (SPE), supercritical
fluid extraction (SFE) and cloud point extraction (CPE).5–10 The
first three methods require high concentrations of toxic organic
solvents, and are time-consuming. The latter two methods
require considerably less solvent, but are expensive and
complicated procedures. On the other hand, a good alternative
to these methods is cloud point extraction (CPE), where PAHs
extraction is done with nonionic surfactants based on the cloud-
point phenomenon. The surfactant-rich phase obtained in the
separation process is compatible with both micellar and
hydroorganic mobile phases and with the common carrier used
in the HPLC or FIA methodology. CPE offers high
preconcentration factors, safety, and lower costs on PAHs
pretreatment.
Solid-phase microextraction (SPME) is a new, fast and simple
extraction technique that uses coated silica fiber to extract
organic compounds from aqueous or gaseous samples.
Pawliszyn et al. first proposed SPME,11 and which has been
subsequently applied to the trace determination of organic
micro-pollutants, such as volatile organic compounds (VOCs),12
phenol,13 polychlorinated biphenyls (PCBs)14 and pesticides.15
Recently, solid-phase microextraction has been used for the
extraction and concentration of PAHs,16 since it is fast and
effective, requires little chemical solvent and produces little
waste effluent. Since only little of the solvent is required, there
is minimal toxic exposure to technicians when SPME is used.
This SPME is a good method to extract PAHs in water.
In addition, the concentration of aqueous-phase PAHs is
considerable at ng/l levels or below in authentic environments.
1384
Because of this, several analytical techniques have been
developed to measure low concentrations of PAHs in water.
The analysis of these compounds can be performed by various
gas-chromatographic,17 high-performance liquid
chromatographic18,19 and electrophoretic methods.20 Gas
chromatography with a flame ionization detector (FID) offers
some degree of sensitivity and selectivity for PAHs compounds.
However, the detector often experiences severe interference and
loss of sensitivity in complex environmental matrices. GC
coupling with MS system affords high sensitivity and high
resolution, but requires an expensive and complex procedure.
The already-mentioned GC/MS method is not satisfactory for
routine analysis. Thus, the high-performance liquid
chromatographic method is still widely used to determine
environmental PAHs. The advantage of high-performance
liquid chromatography for the fractionation of PAH mixtures
and sample clean-up are undoubted and validated.18 High-
performance liquid chromatography coupled with fluorescence
detection has been used for analysis of some environmental
samples. The technique of efficient separation has been
described in several papers.21,22
This paper explores the potential of the SPME-HPLC-FLD
method for determining the concentration of PAHs in aqueous
environments, since SPME was developed as an effective
pretreatment method to extract five PAHs from water. In this
report, the SPME parameters and optimum conditions for
HPLC/FLD analysis of water phase PAHs are discussed in detail.
Experimental
Chemicals and reagents
The major PAH compounds include pyrene (abbreviated,
Pyr), benzo[k]fluorathene (B[k]F), benzo[a]pyrene (B[a]P),
benzo[ghi]perylene (B[ghi]Pe), dibenzo[a,e]pyrene (DB[a,e]P).
Since the above PAHs can usually enter surface water via
atmospheric fallout and rain-out in Taiwan, we selected the five
PAHs as the object compounds for this paper. The main
chemicals were purchased from TCI (Tokyo, Japan), such as
benzo[b]fluoranthene, benzo[a]pyrene, and dibenzo[a,e]pyrene.
Pyrene was purchased from Supelco (Bellefonte, PA, USA).
Benzo[ghi]perylene was obtained from Aldrich (Milwaukee,
WI, USA). All chemicals were HPLC-grade reagents. The
solvents acetonitrile and hexane were obtained from Fisher
(HPLC grade, Springfield, MO, USA). The salt compounds,
including sodium monochloroactate (ClCH2COONa), sodium
chloride (NaCl), potassium chloride (KCl), potassium carbonate
(Na2CO3), sodium sulfite (Na2SO3), were purchased from Fluka
(Gallen, Switzerland). Purified water (conductivity > 18
MΩ/cm) was distilled and deionized using a Millipore 60
system (Bedford, MA, USA), and used for all aqueous
solutions. PAH stock solutions (0.05 mM) were prepared by
dissolving five PAHs of pure analytes in acetonitrile. In order
to prevent the decay of PAHs, all of the solutions were stored in
brown bottles, and refrigerated at –20˚C until each analysis.
Solid-phase microextraction procedures
The fiber assemblies purchased were coated with 30 µm of
polydimethylsiloxane (PDMS). The fiber was conditioned in a
desorption chamber of the SPME-HPLC interface for 30 min
before initial use, according to the supplier’s instructions. After
conditioning, SPME was carried out by placing 10 ml of water
samples into vials. The samples were saturated with 1.5 M
ClCH2COONa, and then heated at 80˚C with a magnetic stirring
bar for 35 min, at a constant speed of 900 rpm. The analytes
ANALYTICAL SCIENCES OCTOBER 2004, VOL. 20
were desorbed from the fiber, and then injected into the HPLC
system with the commercial SPME-HPLC interface. Because
actual environmental water samples contained some particulate
interference, they must be filtered through a 0.45 µm membrane
filter (Whatman, Maidstone, UK) before extraction.
Apparatus
The high-performance liquid chromatography (HPLC) system
consisted of two pumps (SCL-6B) (Shimadzu, Kyoto, Japan)
equipped with a 6-port valve (M7125, Rheodyne, CA, USA)
adapted with a reverse-phase Supelcosil LC-PAH analytical
column (150 × 4.6 mm i.d.; Bellefonte, PA, USA). For this,
80% acetonitrile + 20% 0.01 M sodium monochloroacetate
were used as a mobile eluent at a flow-rate of 1.0 ml/min. A
programmable fluorescence detector (FLD-6A, Shimadzu,
Kyoto, Japan) was used to quantify analytes, and the
chromatographic data were treated by a Chem. Win 1.0 data
system (Taipei, Taiwan). The duct assembly used stainless-
steel tubing to prevent the permeation of oxygen into the mobile
eluent. The column temperature was set at 45˚C in a
thermostatically controlled oven (Shimadzu Model CTO-6A).
Environmental sampling
During the winter of 2003, thirty water samples were
collected from Cheng Ching Lake in Kaoshiung City of
southern Taiwan, which is an important drinking-water source
near the petrochemical districts of Kaoshiung. The depth of
sampling was about 1.5 m. The distance of the sampling site
was about 10 m away from the lake bank. Water samples were
collected in amber glass bottles, which are essential to prevent
decay due to ultraviolet radiation. These bottles had Teflon-
lined tops, which are generally recommended for sampling
organic compounds. The sampling apparatus and the glassware
were pre-cleaned and rinsed with acetonitrile and hexane to
remove any polar and non-polar compounds. After returning to
the laboratory, aliquots of the samples were filtered through a
membrane filter under vacuum to obtain dissolved samples for
PAH determination. Finally, each sample was refrigerated at
–20˚C until the SPME procedure.
Calibration and recovery tests
The stock standard solution was prepared by dissolving 1 mg
of each compound in 100 ml acetonitrile, and calibration
standards of 0.01 – 65 µg/l (n = 9) were prepared from the stock
solution of 1 mg/l. Spiked samples were prepared by the
addition of aliquots (1 ml) of 2.40 µg/l PAH standard solutions
to 10 ml of lake samples. The spiked samples were treated by
the extraction and analysis procedures described above. The
recovery yield was calculated by dividing the slope of the linear
regression for spiked samples by that for standard solutions in
the same concentration range. Reagent analyses were used to
ensure that no PAHs were present in laboratory reagents, fibers,
or other interferences.
Results and Discussion
Optimization parameters of solid-phase microextraction
Several experimental parameters were examined in order to
improve the speed, sensitivity, and selectivity of SPME.
Attention to seemingly minor details can often contribute
greatly to the success of the PAH analysis. The five parameters
of SPME are discussed in the following sections.
ANALYTICAL SCIENCES OCTOBER 2004, VOL. 20
Fig. 1 Extraction temperature profile for the peak area of PAHs.
The extraction time and PAH concentrations were 35 min and 1 µg/l,
respectively.
Effect of the extraction temperature
The extraction temperature potentially has several effects on
the SPME process. Firstly, increasing the temperature during
the extraction process may enhance the diffusion of the PAH
analytes towards the fiber, thus decreasing the equilibrium time.
Furthermore, increased temperature can improve PAH analytes
evaporation rates and mass transfer at the water-gas the
interface.23 After testing, the effects of the extraction
temperature were obtained, as shown in Fig. 1, indicating the
extraction yield (expressed as peak area) passes through an
optimal value at 80˚C. Before this temperature, the extraction
yield increases with increasing temperature due to enhanced
mass transfer, whereas at temperatures above the optimal value,
the uptake decreases or levels off due to thermodynamic reasons
when decreasing the distribution constant. The same trend of
the temperature effect is apparent in other PAH compounds.
Ion species and strength effect
The addition of a salt to an aqueous sample shifts the partition
equilibrium so that more of the analytes will be extracted. The
ionic strength has been reported for several analytes, with
enhancements of their absorption on the fiber. A composite
effect of ionic strength in solution has been defined as follows:
where Ci is the concentration of i in moles per liter and Zi is
charge on species i. To obtain the maximum extraction yield, it
is important to select an optimal salt in the ion species effect. In
the present work, we tried to test five commercial salts at the
same ionic strength of 1.5 M. Furthermore, a pioneering
salting-out test was performed by using the ClCH2COONa
organic salt. We were the first to develop organic salts for
solid-phase microextraction. It is an important reason to
simultaneously consider improving the efficiency for analysis
and extraction. Sodium monochloroacetate (an organic salt) is
often used as a buffer system in the mobile phase of liquid-
chromatographic separation. Kuo22 and Long24 et al. indicated
that the use of sodium monochloroacetate can improve the
stability, resolution, and sensitivity of organic analytes. Sodium
monochloroacetate was simultaneously used as an eluent buffer
and extract accelerant in the present work. The object of the
section is to compare the difference of extraction yield in salt
species between inorganic salts (KCl, NaCl, Na2SO3, and
Na2CO3) and organic salt (ClCH2COONa). The results are
demonstrated in Fig. 2, where the peak area of the extraction
yield is plotted against the PAH species. One particular
discovery is that sodium monochloroactate has a maximum than
1385
Fig. 2 Ion species effect for five PAHs by SPME-HPLC analysis at
the same 0.15 M ClCH2COONa ionic strength. The extraction time,
extraction temperature and PAH concentrations were 35 min, 80˚C,
2.4 µg/l, respectively.
Fig. 3 Ion-strength dose response for PAHs against sodium
monochloroactate. The extraction time, extraction temperature and
PAH concentrations were 35 min, 80˚C, 2.4 µg/l, respectively.
common inorganic salts at 1.5 M ionic strength, B[ghi]Pe,
DB[a,e]P especially. The potential reason is that ClCH2COONa
improves the organic PAHs’ dissociation from an aqueous
solution and subsequent adsorption into SPME fiber. Sodium
monochloroacetate is expected to have a high activity
coefficient of the ion species for semi-volatile PAH compounds,
and thus improve the PAHs’ dissociation. A following study
was carried out to accurately quantify the dose-response
between the peak area and sodium monochloroacetate
concentrations ranging from 0 – 9 M. The results are shown in
Fig. 3. It is clear that 1.5 M sodium monochloroactate produces
the maximum ion strength effect on the extraction yield (peak
area). Since this leads to the best extraction yield, that dose will
be adopted in subsequent experiments.
Extraction-time profile
The dependence of the extracted amount of analyte on the
extraction time gives valuable information for this extraction
method development, and allows for the experimental
determination of the equilibration time. The extraction-time
profiles for the PAH compounds were obtained for 5 ml spiked
solutions with 1.0 µg/l of PAHs by detecting the peak area of
the signal. The experiment was controlled under the condition
of 1.5 M sodium monochloroacetate, 80˚C, and a constant
stirring speed. Figure 4 shows the time dependence for five
1386
Fig. 4 Exposure time profile for PAHs extraction by SPME-HPLC
analysis. The extraction temperature, ion strength of ClCH2COONa
and PAH concentrations were 80˚C, 1.5 M, 2.4 µg/l, respectively.
Fig. 5 Effect of the stirring speed for PAHs by SPME-HPLC
analysis. The extraction time, extraction temperature, ion strength of
ClCH2COONa and PAH concentrations were 35 min, 80˚C, 1.5 M,
2.4 µg/l, respectively.
compounds, and it is apparent that the extraction time profile
depends on individual analytes. For the PDMS fiber, the
equilibrium for all selected compounds was nearly reached at 35
min. No significant increase occurred at 35 – 120 min. Much
longer equilibrium times are not necessary, because the
extraction yield (peak area) have reached a plateau. The
extraction was selected at 35 min, and for future quantitative
analysis, an exposure time of 35 min is a reasonable value for a
good peak response at a logical assay time.
Effect of stirring speed
Since SPME was based on the equilibrium distribution
progress, the maximum amount of analytes would be extracted
at the equilibrium time. Stirring of aqueous samples could
reduce the time to reach equilibrium by enhancing the diffusion
of analytes towards the fiber. Thus, the stirring speed of the
aqueous solution was an important parameter. Signals of the
studied PAHs were measured from spiked samples in the
presence of 1.5 M sodium monochloroactate, 35 min extraction
time, and heated to 80˚C at various stirring speeds. As shown in
Fig. 5, it is apparent that all of the PAH signals slowly increase
with the stirring speed, reaching a plateau and remaining
constant. The sample stirring speed of 900 rpm was the optimal
condition and was used throughout.
ANALYTICAL SCIENCES OCTOBER 2004, VOL. 20
Fig. 6 Effect of pH for PAHs by SPME-HPLC analysis. The
extraction time, extraction temperature, ion strength of
ClCH2COONa, stirring speed and PAH concentrations were 35 min,
80˚C, 1.5 M, 900 rpm, 2.4 µg/l, respectively.
Effect of pH
In the SPME, as any extraction method, the pH of the sample
can be adjusted to provide better selectivity. The optimal pH is
related to the PAH characteristics. In our study, experiments
were carried out with sample solutions from pH 4.0 to pH 8.0
(Fig. 6). A strong dependence of the extraction yield on the pH
value was observed. Comparing the five PAH compounds, the
best extractions were at low pH, and the maximum at pH 6.0.
Studies by Yang25 and Pawliszyn26 had confirmed that adjusting
the pH of an aqueous would change K for dissociable species,
and affect the extraction efficiency. Furthermore, a study by
Madichie et al.27 indicated that an appreciate pH improved
extraction efficiency. The range of pH 6 – 8 can reach a
maximum yield of PAHs compounds and reflect the authentic
surface water. Reports already mentioned in this paper can
explain that a dependence of maximum extraction efficiency on
pH 6.0 is reasonable and acceptable.
SPME efficiency
The test series described above indicated the optimal
parameters of SPME, including the extraction temperature,
time, ionic strength, stirring speed, and pH. To identify the
SPME efficiency of these analytes, spiked samples of 1.0 µg/l
PAHs were determined by the SPME-HPLC-FLD system under
the optimal conditions of SPME at 1.5 M sodium
monochloroactate, 80˚C, pH 6.0, 900 rpm, and a duration of 35
min. Under the above optimized condition, the recovery yields,
relative standard deviation (RSD) and validation of spiked-
sample peak area were tested, with results as shown in Table 1.
The recovery yields were good, ranging from 88 – 98%. The
RSDs of extraction reproducibility were all within 5%. The
extraction efficiencies of SPME method were good, meeting the
requirement for accuracy and precision for the purpose of
environmental determination. The extraction efficiency is good
and acceptable for routine environmental analysis.
Selection of the fluorescence condition for PAHs
It is essential to select a suitable wavelength with the best
sensitivity to measure the amounts of individual PAHs. The
detection wavelengths were indicated by a rapid fluctuating-
scan function. The optimal sensitivity parameters for measuring
the PAH constituents are listed in Table 2. The highest
intensities of fluorescence were observed at wavelength pairs of
excitation and emission: pyrene 237 nm/436 nm,
benzo[k]fluoranthene, benzo[a]pyrene 266 nm/415 nm,
ANALYTICAL SCIENCES OCTOBER 2004, VOL. 20 1387

Table 1 Recovery yield and validation of spiked water

samples with SPME and HPLC-FLD
Recovery R.S.D., Peak area
PAH compound
yield, % % R.S.D., %

Pyrene 88.7 2.3 1.2

Benzo[k]fluoranthene 93.4 3.5 2.5
Benzo[a]pyrene 89.1 3.0 2.2
Benzo[ghi]perylene 97.8 4.0 4.1
Dibenzo[a,e]pyrene 98.0 4.8 4.5

1 ml, 2.40 µg/l of each PAH, n = 10.

Table 2 Fluorescence optimal characteristics of selected PAH

compounds at a fluorescence detector

Maxima/nm
PAH compound
Excitation Emission
Pyrene 237 436
Benzo[k]fluoranthene 266 415
Fig. 7 Typical HPLC-FLD chromatograms of PAH standards and
Benzo[a]pyrene 266 415
lake-water samples after SPME. (A) Standards: Pyr, B[k]F, B[a]P,
Benzo[ghi]perylene 295 410
B[ghi]Pe, and DB[a,e]P, respectively (0.81 µg/l). (B) Run sample:
Dibenzo[a,e]pyrene 306 398
the chromatogram of a sample obtained using SPME-HPLC-FLD
method.

Table 3 Calibration plots and analytical features for the

benzo[ghi]perylene 295 nm/410 nm and dibenzo[a,e]pyrene 306 determination of PAHs in water using SPME and high-
nm/398 nm. The retention times of individual PAHs were performance liquid-chromatography with fluorescence detection
acceptable in the range of 9 – 24 min. The retention times were Calibration
9.3, 13.9, 15.3, 20.9 and 23.3 min for Pyr, B[k]F, B[a]P, PAH compound Linearity/r LODa/ng l–1
range/µg l–1
B[ghi]Pe, and DB[a,e]P, respectively.
Pyrene 0.01 – 65 1.0000 3.4
Linearity, precision and detection limits Benzo[k]fluoranthene 0.01 – 65 0.9999 2.3
The linearity of the method was tested by SPME-HPLC-FLD Benzo[a]pyrene 0.01 – 65 0.9999 4.2
Benzo[ghi]perylene 0.01 – 65 0.9998 6.0
determining aqueous standards, with increasing concentration, a
Dibenzo[a,e]pyrene 0.01 – 65 0.9999 5.1
calibration range from 0.01 – 65 µg/l of PAHs standards (n = 9).
Table 3 gives calibration plots and analytical features for a. Limit of detection (S/N = 3).
determination of PAHs in water using SPME and high-
performance liquid chromatography with fluorescence detection
and calibration range, the linearity and detection limit (LOD) of
individual PAHs. Least-squares linear regression analysis was spots were 1.02, 0.72, 0.28, 1.20, and 0.54 µg/l for Pyr, B[k]F,
used to evaluate the linearity. The table results show a good B[a]P, B[ghi]Pe, and DB[a,e]P, respectively. The
linear behavior in the tested range with the linear correlation concentrations of pyrene and benzo[ghi]perylene were higher
coefficients (r) ranging between 0.999 and 1.000. than that of the other compounds. A consistent trend was
The LOD of an assay, for five PAHs, was calculated confirmed by a previous report,28 and was related to the Kow,
according to the expression LOD = 3 (SEb + b)/a, where SEb is vapor pressure of PAH characteristics. The total PAH
the standard error of the intercept, b the intercept, and a the concentration was in the range of 3.01 – 4.38 µg/l. A
slope. The detection limits (ng/l) were 3.4, 2.3, 4.2, 6.0 and 5.1 comparison of the present results to those of other published
for Pyr, B[k]F, B[a]P, B[ghi]Pe and DB[a,e]P, respectively. studies revealed that the PAHs concentrations are higher than
The detection limits achieved in present work are comparable to those of Aach River (Germany)29 and Trent River (UK),29 but
the detection limits reported by EPA Methods USA 8270 and are lower than Jiulong River (China).30 The major contributor
published values.23 Low LOD sufficiently determined the low to the PAHs levels is refinery or petrochemical industry
level PAHs in authentic water samples. To evaluate the effluents, because Cheng-Ching Lake is a reservoir to the
feasibility of this method, the SPME-HPLC-FLD application of neighboring petrochemical industry region. PAHs levels of
monitoring real samples will be described in the next section. Cheng-Ching Lake are normal and acceptable in this paper.
However, because this level of lake water exceeds the EU
PAH concentration in urban raw drinking water drinking standard,3,4 it is necessary to further monitor the PAH
The effectiveness of the proposed method was actually tested concentrations of tap water through purity treatment in order to
on lake-water samples. Thirty real samples were sampled from insure the health of residents.
Cheng Ching Lake, which is an important drinking-water source
for Kaoshiung City of southern Taiwan. The monitored results
for real samples by the SPME-HPLC-FLD determination Conclusion
ranged from 0.18 – 1.32 µg/l for PAHs, as listed in Table 4. The
mean concentrations of thirty samples from different sampling Solid-phase microextraction is a very simple, rapid, sensitive,
1388 ANALYTICAL SCIENCES OCTOBER 2004, VOL. 20

Table 4 Comparison of the PAHs concentration in surface water between Taiwan and other countries (µg l–1)
Cheng-Ching Lake Aach River29 Trent River29 Jiulong River30
PAH/µg l –1 (Taiwan, this study) (Germany) (UK) (China)
Range Mean Range Range Range
Pyrene 0.84 – 1.23 1.02 0.22 – 2.66
Benzo[k]fluoranthene 0.66 – 0.80 0.72 0.13 – 0.17 0.03 – 0.26 0.30 – 2.05
Benzo[a]pyrene 0.18 – 0.35 0.28 0.01 – 0.04 0.05 – 0.50 0.56 – 3.32
Benzo[ghi]perylene 0.91 – 1.32 1.20 0.04 – 0.11 0.07 – 0.69
Dibenzo[a,e]pyrene 0.42 – 0.68 0.54
Total PAH 3.01 – 4.38 3.76

and accurate technique for the extraction of nonpolar polycyclic
hydrocarbons from water samples. High recovery and good
reproducibility were obtained using 30 µm of
polydimethylsiloxane (PDMS) fiber in this study. The
optimized SPME procedure can be used instead of other
methods, or conventional liquid-liquid extraction, which are
more complicated, time-consuming, and liable to
contamination. The optimal operating conditions for SPME are
1.5 M sodium monochloroactate, 80˚C, pH 6.0, 900 rpm, and a
duration of 35 min. A particular discovery is that 0.15 M
sodium monochloroactate (ClCH2COONa) can improve the
extraction yield of PAH compounds more than other inorganic
salts. The linearity of SPME is very good, and the detection
limits are generally at a low ng/l level with HPLC/FLD. The
accuracy and precision of the SPME-HPLC-FLD technique are
satisfactory for quantitative the routine analysis of PAHs in
aqueous samples. The technique provides a relatively simple,
convenient, practical procedure that has been successfully
applied to determine authentic PAHs samples in an aqueous
environment. In the future, this technique can be applied to the
real-time monitoring of drinking quality and safety. It is
important to determine the PAH levels of daily consumable
water and household drinking water after a water-purification
procedure, and to further evaluate health risks to people.
References
1. R. G. Harvey, “Polycyclic Hydrocarbons and
Carcinogenesis”, 1985, American Chemical Society,
Washington, D.C.
2. IARC Monograph, International Agency for Research on
Cancer, 1983, Vol. 32, Lyon.
3. European Economic Community, Office Journal of the
European Communities Council, “Quality of Water
Intended for Human Consumption”, 1980, Vol. 229,
Luxemburg, 11.
4. D. Djozan and Y. Assadi, Microchem. J., 1999, 63, 276.
5. E. R. Noordkamp, J. T. C. Grotenihuis, and W. H. Rulkens,
Chemosphere, 1997, 35, 1907.
6. Y. F. Song, X. Jing, S. Fleischmann, and B. M. Wilke,
Chemosphere, 2002, 48, 993.
7. D. Barceló, J. Chromatogr., 1993, 643, 117.
8. C. Aguilar, F. Borrull, and R. M. Marcé, J. Chromatogr. A,
1997, 771, 221.
9. S. A. Wise, L. C. Sander, and W. E. May, J. Chromatogr.,
1993, 642, 329.
10. C. G. Pinto, J. L. P. Pavón, and B. M. Cordero, Anal.
Chem., 1994, 66, 874.
11. C. L. Arthur and J. Pawliszyn, J. Anal. Chem., 1990, 62,
2145.
12. F. J. Santos, M. T. Galceran, and D. Fraisse, J.
Chromatogr. A, 1996, 742, 181.
13. P. Bartak and L. Cap, J. Chromatogr. A, 1997, 767, 171.
14. D. W. Potter and J. Pawliszyn, Environ. Sci. Technol.,
1994, 28, 298.
15. M. T. Sng, F. K. Lee, and H. A. Lakso, J. Chromatogr. A,
1997, 759, 225.
16. J. Chen and J. B. J. Pawliszyn, Anal. Chem., 1995, 67,
2530.
17. F. J. Sntos and M. T. Galceran, Trends Anal. Chem., 2002,
21, 672.
18. C. Mao and A. A. Tucker, J. Chromatogr. A, 2002, 966, 53.
19. F. Sun, D. Littlejohn, and M. D. Gibson, Anal. Chim. Acta,
1998, 364, 1.
20. A. L. Nguyen and J. H. T. Lung, Anal. Chem., 1997, 69,
1726.
21. F. Lai and L. White, J. Chromatogr. A, 1995, 692, 11.
22. C. T. Kuo, H. W. Chen, and S. T. Lin, Anal. Chim. Acta,
2003, 482, 219.
23. L. Hou and H. L. Lee, J. Chromatogr. A, 2002, 976, 377.
24. H. Long, Y. Zhu, M. Cregor, F. Tian, and L. Coury, J.
Chromatogr. A, 2002, 47, 933.
25. X. Yang and T. Peppard, LC-GC, 1995, 882, 13.
26. J. Pawliszyn, “Theory and Practice”, 1997, Wiley-VCH,
Inc.
27. C. Madichie, G. M. Greenway, and T. McCreedy, Anal.
Chim. Acta, 1999, 392, 39.
28. R. K. Sorrell, H. J. Brass, and R. Reding, Environ. Int.,
1980, 4, 245.
29. E. Manoli and C. Samara, Trends Anal. Chem., 1999, 18,
417.
30. K. Maskaoui, J. L. Zhou, H. S. Hong, and Z. L. Zhang,
Environ. Pollut., 2002, 118, 109.