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Abstract
A systematic study was made on the identification and quantitative determination of polynuclear aromatic hydrocarbons (PAHs) in heavy products
derived from coal and petroleum with high performance liquid chromatography (HPLC). After the separation of PAHs by a high-resolution column,
identification was made through four methods: (1) the relative retention time (RRT) method, (2) the stop-flow-UV scanning method, (3) the method
of fluorescence characteristic index Φ and (4) the method of V index at different UV wavelengths. For the quantitative determination of the
components, methods of external standard (E-X), internal standard (I-N) and external standard-response factors (E-F) were compared. The E-F
method was recommended by the present paper. For the determination of quantitative response factors (F) two methods were studied, including
the HPLC peak-area method (Peak-area method) and the UV absorbance method using a UV spectrometer (absorbance method). The absorbance
method was better and is recommended by the present paper. The F values of 30 PAHs from the two different methods are given. The samples
analyzed include a coal tar pitch, a thermal cracking residue oil and a residual oil from ethylene production.
© 2007 Elsevier B.V. All rights reserved.
Keywords: High performance liquid chromatography; Polynuclear aromatic hydrocarbons; Identification and quantitative determination
0021-9673/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2007.08.048
172 C. Zhang et al. / J. Chromatogr. A 1167 (2007) 171–177
Table 1
Name and source of practical samples
No. Name Source
2. Experimental
Sxλ
V = (2)
Sx254
Identification of peaks:
Fig. 5. Comparison of UV spectra of fluoranthene and pyrene with the UV spectra of peaks (components) no. 8 and no. 10 in Fig. 4. A1-sample: peak no 8 of Fig. 4.
A2-pure reagent: fluoranthene. B1-sample: peak no 10 of Fig. 4. B2-pure reagent: pyrene.
Table 4
V values of components in an petroleum ether extract of coal tar pitch compared with those of pure reagents
Peak no in Fig. 4 Compound Pure 290/254 (nm) Sample 290/254 (nm) Pure 270/254 (nm) Sample 270/254 (nm)
should be performed at the same conditions. The F factors Figs. 1–4 indicate high resolution for either pure PAHs or
of each component were calculated from their peak areas practical samples. Compared with the analysis of similar sam-
by the following equation: ples [8–13], Fig. 3 is superior in clarity and resolution. The
same trend was observed in comparing the chromatogram of a
[Sx /Wx %] petroleum ether extract of coal tar pitch (Fig. 4) with a similar
Fx = (4)
[Sph /Wph %] analysis found in reference [12].
where Fx is the F value of component x, Sx and Sph are peak
3.2. Qualitative results
areas of component x and phenanthrene, respectively, and
Wx % and Wph % are the percentage contents of component
3.2.1. Identification by RRT
x and phenanthrene.
In this paper, all the samples in Table 1 were analyzed in this
(2) UV absorbance method
way. As this method is one of the methods widely used in the
PAH solutions of known concentrations were prepared
identification of components in chromatographic analysis, it is
and the UV absorbance of each hydrocarbon was determined
not necessary to list the detailed data of RRT here.
by a UV spectrometer. At the same wavelength (λ254 nm),
F values were calculated from the following equation
3.2.2. Identification by stop-flow UV scanning
[Ax /Wx %] The identification of fluoranthene and pyrene in petroleum
Fx = (5)
[Aph /Wph %] ether extract of coal tar pitch by this method is shown as exam-
ples in Fig. 5A and B, respectively. It can be seen that the
where Fx is the F value of component x, Ax and Aph are the ultraviolet spectra of components in samples are exactly identi-
UV absorbance of component x and phenanthrene, respec- cal with those of corresponding pure reagents.
tively, and Wx % and Wph % are the known concentrations of This method is reliable, but requires a larger injection size (for
component x and phenanthrene, respectively. example, 15 l or 20 l), and only one component is identified
in each run.
3. Results and discussions
3.2.3. Identification by fluoresbene characteristic Ф index
3.1. Separation of PAHs Typical examples of this method are shown in Figs. 1–3. In
Fig. 2, the UV wavelength is 254 nm, fluorescence excitation
By applying a high-resolution chromatographic column wavelength (Ex ) is 380 nm and emission wavelength (Em ) is
under a series of optimal chromatographic conditions, the reso- 460 nm.
lution of the critical pair of phenanthrene/acenaphthene was 5, At wavelengths of “Ex = 265 nm, Em = 370 nm”;
which is better than literature values [8–13]. “Ex = 250 nm, Em = 380 nm”; “Ex = 336 nm, Em = 374 nm”;
176 C. Zhang et al. / J. Chromatogr. A 1167 (2007) 171–177
Table 5
Response factors of PAHs determined by different methods
No Component Absorbance method HPLC method Average Deviation (%)
and “Ex = 250 nm, Em = 315 nm”; components having high Compared with UV scanning method, the V method is supe-
responses are chrysene, anthracene, pyrene and benzene rior in that it does not require high component concentrations
homologues, respectively. and saves much labor.
By changing Ex and Em and comparing the Ф indexes with
those of pure reagents, each of the components can be effectively 3.2.5. Comparison of different qualitative methods
identified. Based on the data presented above, each method has its advan-
Typical comparisons of Ф indexes of PAHs in residual oil tages and disadvantages. The multi wavelength UV method
from ethylene production and thermal cracking residual oil are supplements the stop-flow UV scanning method which is reli-
listed in Tables 2 and 3, respectively. From the tables, it can able but laborious. For the analysis of complex samples from
be seen that different PAHs have different Ф indexes, and the coal and petroleum, a combination of different methods is more
method shows a high selection specificity. The Ф indexes of desirable.
benzo[a]pyrene, chrysene, perylene, and coronene are all very
large. The Ф indexes of the components are very close to those
3.3. Quantitative results
of the pure reagents. Therefore, the identification of the peaks
is reliable.
3.3.1. Response factors (F) of PAHs
Response factors of 30 PAHs determined by the HPLC
3.2.4. UV characteristic index V method peak area method and/or UV absorbance method are listed in
Typical results with this method are shown in Fig. 4 and listed Table 5. From this table it can be seen that the deviation between
in Table 4 for a petroleum ether extract of coal tar pitch. HPLC method and UV absorbance method was small. The UV
From Fig. 4, it is clear that the response of a PAH is absorbance method was quick and convenient.
greatly different at different UV wavelengths. From Table 4,
for most PAHs, the ratio of responses at different wave- 3.3.2. Quantitative results of typical practical samples
lengths in pure state is fairly close to that in practical The quantitative analyses results of “Daqing” thermal crack-
samples. ing residual oil by the E-F method are listed in Table 6. From
C. Zhang et al. / J. Chromatogr. A 1167 (2007) 171–177 177